Performic acid biofilm prevention for industrial CO2 scrubbers

ABSTRACT

Peroxyformic acid compositions for removal of biofilm growth and other contaminants and impurities from industrial processing hard surfaces are disclosed. In particular, peroxyformic acid compositions may be dosed on site and/or generated in situ for the reduction and prevention of biofilms on the hard surfaces. Methods of employing the peroxyformic acid compositions for removal of biofilm growth and other impurities such as aldehydes and alcohols from industrial CO2 effluent are also disclosed which beneficially provide ambient biofilm control and break down more rapidly than other peracids, allowing for extended runs between CIP cleaning, including a reduction and/or elimination of cleaning of the scrubbers and other industrial surfaces.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Continuation Application of U.S. Ser. No. 16/362,885, filedMar. 25, 2019, which is a Continuation Application of U.S. Ser. No.15/487,641, filed Apr. 14, 2017, now U.S. Pat. No. 10,278,392, issuedMay 7, 2019, which claims priority under 35 U.S.C. § 119 to provisionalapplication Ser. No. 62/323,024, filed Apr. 15, 2016, titled “PerformicAcid Biofilm Prevention For Industrial CO₂ Scrubbers,” which is hereinincorporated by reference in its entirety.

FIELD OF THE INVENTION

The invention relates to use of peroxyformic acid compositions forremoval of biofilm growth and other impurities such as aldehydes andalcohols from industrial CO₂ effluent. Accordingly, the presentinvention relates to the field of biofilm control and CIP cleaning ofscrubbers and other industrial surfaces. In particular, peroxyformicacid compositions can be generated in situ or on site or provided in apre-formed composition for the reduction, removal and/or kill ofbiofilms and the mitigation of other impurities on such hard surfaces.The compositions according to the invention beneficially provide ambientbiofilm control and break down more rapidly than other peracids,allowing for extended runs between CIP cleaning, including a reductionand/or elimination of cleaning of the scrubbers and other industrialsurfaces.

BACKGROUND OF THE INVENTION

Industrial processing surfaces, including scrubbers, are conventionallytreated using clean-in-place (CIP) methods to provide flushing, rinsing,pretreatment, cleaning, disinfecting, sanitizing and preserving, inorder to prevent fouling during processing. Fouling components anddeposits can include inorganic salts, particulates, microbials andorganics. Fouling manifests itself as a decline in performance and/orquality of the finished goods. Fouling can also include biofilm growthalong with other impurities within industrial processing systems, suchas CO₂ scrubbers employed in ethanol and other fermentation systems,having detrimental results. As a result, CIP processes are utilized tocirculate cleaning agents over and through the industrial processingsurfaces to wet, penetrate, dissolve and/or rinse away foreignmaterials. Various parameters that can be manipulated for cleaningtypically include time, temperature, mechanical energy, chemicalcomposition, chemical concentration, soil type, water type, andhydraulic design. Conventional cleaning techniques include the use ofhigh heat and/or extreme pH, i.e., very high alkalinity use solutions,or very low pH acidic use solutions. However, many surfaces cannottolerate such conditions.

In an exemplary industrial processing, CO₂ scrubbers are often used toremove impurities such as aldehydes and alcohols from the industrialeffluent by spraying water through a column packed with porous spheresof HDPE plastic to improve surface contact. However, over time, biofilmsform inside the scrubbers, causing plugging, fouling, reduction ofoptimal flow, and potential contamination of the upstream process incases where ethanol (EtOH) is reclaimed back into the process that hasbeen carried out with the CO₂. Such biofilm growth and impurities, suchas aldehydes and alcohols, need to be removed from industrial surfacesto prevent severe decline in production and operation of the systemswhich can also negatively impact the quality of finished goods, andoften premature replacement of such industrial processing systems.

Among various biocides known, peroxycarboxylic acids are increasinglyused as antimicrobials and bleaching agents in many applications, owingto their high efficacy against a broad spectrum of microorganisms, colorsafe property, low residues and nontoxic nature of their decompositionproducts. Peracetic acid is the most commonly used peroxycarboxylic acidand has been shown to be a good biocide, but only at relatively highconcentrations (generally greater than 80 part per million). Similarly,peroxyfatty acids have also been shown to be biocidal, but only at highconcentrations (greater than 200 ppm), such as in the compositiondisclosed in European Patent Application No. 233,731. In contrast,peroxyformic acid has an advantageous degree and range of microcidalproperties compared to other peroxycarboxylic acids, such as peraceticand perproprionic acids, as disclosed by V. Merka et al in J. Hyg.Epidem. Microbiol. Immunol, 1965 (IX) 220, as well as in European PatentApplication No. 863,098,96.

Although various agents preventing microbial growth, such as oxidizersand biocides, are known for cleaning industrial processing surfaces,including CIP cleaning techniques, there is still a need for an improvedmethod for the prevention of microbial growth and biofilm formation.

Biofilms are biological conglomerates that contain pathogens, such asbacteria and other microorganisms, embedded in a matrix of exopolymersand macromolecules. In addition to bacteria, other microorganisms arecommonly found in biofilm, including fungi, molds, algae, protozoa,archaea and mixtures of these microorganisms. Biofilms form as a resultof microorganisms establishing on a surface and producing a protectiveextracellular polymeric matrix. Most often biofilm form on surfaces incontact with water, providing a hydrated matrix of polysaccharides toprovide structural protection from biocides, making biofilm moredifficult to kill than other pathogens.

Microbial infection and the formation of biofilm present significantcomplications in numerous industries. Although biofilm are known toexist in a wide-variety of environmental conditions, since biofilm mostoften form on surfaces exposed to bacteria and water, industries such asfood processing are commonly affected by biofilm. For example, theorganism Listeria monocytogenes thrives in cool, damp environments, suchas floor drains, plumbing and other surfaces of food processingfacilities. This provides a potential point of contamination for aprocessing plant environment and food products produced therein.However, biofilm can also develop on inert surfaces of everydayhousehold items. Exposure to such microorganisms through skin-surfacecontact may result in infections and compromise the public's health.Therefore, controlling the formation of biofilm is desirable to decreaseexposure to infectious microorganisms.

Biofilm growth and removal depends on several factors, including thesurface composition and chemical composition of the surroundingenvironment. Several biofilm removal methods are utilized, includingphysical, chemical and biological removal. Means of physically removingbiofilm include the use of magnetic fields, ultra sound, high and lowelectrical fields and abrasive techniques. Physical removal techniquesare often combined with chemical or biological methods, such as biocidesor antimicrobial agents. A number of technologies have been developedthat treat surfaces with organic or inorganic materials to interferewith biofilm development, such as preventing microbial attack anddegradation. For example, coating a surface with or incorporating acomposition into a surface substrate to create a surface whereinmicroorganisms do not adhere or colonize. U.S. Pat. No. 9,072,292.However, such technologies have not effectively eliminated biofilmformation and growth. Therefore, the contamination of surfaces withbiofilm remains a problem.

In light of the foregoing, there remains a demand for compositions andmethods for reducing and removing biofilm.

Accordingly, it is an objective of the claimed invention to provideperoxyformic acid compositions, including those which can be generatedin situ for the prevention and removal of microbial growth andbiofouling from industrial processing surfaces, including CO₂ scrubbers.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

The invention provides a peroxycarboxylic acid composition comprisingperoxyformic acid, which may be generated in situ or on site, for use toremove and/or reduce biofilm growth and other contaminants andimpurities from industrial processing surfaces, including CO₂ scrubbers.Examples of contaminants include for example, particulate matter,organic and inorganic contaminants, oils, process contaminants,microorganisms, and so forth. Suspended matter in the industrialprocesses, and waters associated therewith, provide the microorganismswith readily available nourishment for sustaining life and reproduction.It is well established that the presence of inorganic, organic, andmicrobiological deposits have a detrimental impact on the operationalparameters of an industrial processing system, resulting in reducedefficiency and increased operating cost.

It is an advantage of the present invention that the cleaningcompositions are biodegradable, decompose into non-hazardous productswhich therefore leave no toxic traces on the treated surfaces (due torapid degradation into water, carbon dioxide and formic acid which arerecognized as GRAS) and therefore do not negatively interfere with thefermentation or other products generated within such industrialprocessing surfaces. Moreover, the peroxyformic acid composition issuitable for generation in situ or on site of a point of use, allowing auser to promptly apply the composition to a surface in need oftreatment.

In an aspect, methods of the invention are directed to methods ofremoving biofilm and/or other impurities from industrial CO₂ scrubbers.In a further aspect, the methods of the invention are directed tointermittent treatment of process water streams feeding the industrialprocessing surfaces, such as scrubbers, with the peroxyformic acidcompositions. Beneficially, the peroxyformic acid compositions provideambient biofilm control and removal of other microbial and/or otherimpurities and contaminants, while breaking down rapidly in comparisonto other peracids and peracid compositions.

In an aspect, methods of the invention are directed to methods ofcleaning industrial processing surfaces, such as scrubbers, to provideextended periods of time for processing (or runs) between conventionalclean-in-place (CIP) cleaning methods. In a further aspect, methods ofthe invention are directed to methods of cleaning the industrialprocessing surfaces, such as scrubbers, to reduce and/or eliminate thecleaning of such surfaces.

In a further embodiment, the present invention discloses onsitegenerated peroxycarboxylic acid compositions comprising performic acidthat efficiently kill and removal biofilms and other soils, contaminantsand impurities without damaging or negatively interfering with thetreated surfaces.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation showing the average log reductionof P. aeruginosa biofilm after exposure to the peroxyformic acidformulations according to an embodiment of the invention.

FIG. 2 shows the average log reduction of mesophilic spores afterexposure to the peroxyformic acid formulations according to anembodiment of the invention.

FIG. 3 shows the beneficial performance of peroxyformic acid inanti-biofilm efficacy with shorter exposure time and lowerconcentrations than POAA.

FIG. 4 shows the results of biocidal efficacy of performic acidgenerated in situ according to embodiments of the invention.

FIGS. 5-6 show the results of biocidal efficacy of performic acidcompared to peroxyacetic acid according to embodiments of the invention.

FIG. 7 shows a process diagram depicting an embodiment of the inventionemploying an onsite generated peroxyformic acid for treating a CO2industrial scrubber tower.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention relates to peroxycarboxylic acid compositionscomprising peroxyformic acid, including those which can be generated insitu or on site, for use to reduce and/or prevent biofilm growth andother contaminants and impurities from treated surfaces. The embodimentsof this invention are not limited to particular peroxyformic acidcompositions, which can vary and are understood by skilled artisansbased on the disclosure herein of the present invention. It is furtherto be understood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this invention are presented in a range format. It should beunderstood that the description in range format is merely forconvenience and brevity and should not be construed as an inflexiblelimitation on the scope of the invention. Accordingly, the descriptionof a range should be considered to have specifically disclosed all thepossible sub-ranges as well as individual numerical values within thatrange (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

In some embodiments, substituted alkyls can include a heterocyclicgroup. As used herein, the term “heterocyclic group” includes closedring structures analogous to carbocyclic groups in which one or more ofthe carbon atoms in the ring is an element other than carbon, forexample, nitrogen, sulfur or oxygen. Heterocyclic groups may besaturated or unsaturated. Exemplary heterocyclic groups include, but arenot limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan.

The term “biofilm,” as used herein, means an extracellular matrix inwhich a population of microorganisms are dispersed and/or form colonies.Biofilms are understood to be typically made of polysaccharides andother macromolecules, often referred to as exopolysaccharides, that areconcentrated at an interface (usually solid/liquid) and act as a bindingagent that surrounds such populations of microorganisms. Biofilms arefurther understood to include complex associations of cells,extracellular products and detritus (or non-living particulate organicmaterial) that are trapped within the biofilm or released from cellswithin the biofilm. The term biofilm, as used herein, further refers tothe ASTM definition of biofilm as an accumulation of bacterial cellsimmobilized on a substratum and embedded in an organic polymer matrix ofmicrobial origin. Biofilms are understood to be a dynamic,self-organized accumulation of microorganisms and microbial andenvironmental by-products that is determined by the environment in whichit lives. According to the invention, the phrases “biofilm remediation,”“removing biofilm,” “reducing biofilm” and like phrases, shall mean theuse of the chemical biocide according to the invention which causes areduction in the rate or extent of biofilm growth, removal of existingbiofilm or portions of biofilm on surfaces and/or eradication ofexisting biofilm on a treated surface. According to the invention, thebiocidal compositions disclosed herein physically remove and killbiofilm.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

The term “Distillers Dried Grains” (DDG), as used herein refersgenerally to coproducts of ethanol production by fermentation which cancomprise dried residual grain solids, which can be animal feed grade.“Distillers Dried Grains with Solubles” (DDGS) refers to coproducts ofethanol production by fermentation which can comprise dried residualgrain solids with solubles content, such as process syrup or othersolubles, and which can be animal feed grade. “Wet Distillers Grains”(WDG) refers to coproducts of ethanol production by fermentation whichcan comprise residual grain solids prior to drying, which can contain atleast a portion of process syrup, and which can be animal feed grade.

As it pertains to this disclosure, “fouling” and “contamination” referto the presence or the deposition of any extraneous or undesirableorganic or inorganic material in a water-containing industrial processor onto one or more surfaces within the water-containing industrialprocess. “Microbial fouling” refers to the presence or deposition of anyextraneous or undesirable microbiological organism in a water-containingindustrial process.

The term “generally recognized as safe” or “GRAS,” as used herein refersto components classified by the Food and Drug Administration as safe fordirect human food consumption or as an ingredient based upon currentgood manufacturing practice conditions of use, as defined for example in21 C.F.R. Chapter 1, § 170.38 and/or 570.38.

The term “hard surface” refers to a solid, substantially non-flexiblesurface such as a counter top, tile, floor, wall, panel, window,plumbing fixture, kitchen and bathroom furniture, appliance, engine,circuit board, and dish. Hard surfaces may include for example, healthcare surfaces and food processing surfaces.

As used herein, the terms “mixed” or “mixture” when used relating to“percarboxylic acid composition,” “percarboxylic acids,”“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one percarboxylic acid orperoxycarboxylic acid.

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 50%, or by significantly more than is achieved by a washwith water. Larger reductions in microbial population provide greaterlevels of protection.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 3 log reduction and more preferably a5-log order reduction. These reductions can be evaluated using aprocedure set out in Germicidal and Detergent Sanitizing Action ofDisinfectants, Official Methods of Analysis of the Association ofOfficial Analytical Chemists, paragraph 960.09 and applicable sections,15th Edition, 1990 (EPA Guideline 91-2). According to this reference asanitizer should provide a 99.999% reduction (5-log order reduction)within 30 seconds at room temperature, 25±2° C., against several testorganisms.

As used herein, the term “soil” or “stain” refers to a non-polar oilysubstance which may or may not contain particulate matter such asmineral clays, sand, natural mineral matter, carbon black, graphite,kaolin, environmental dust, etc.

As used in this invention, the term “sporicide” refers to a physical orchemical agent or process having the ability to cause greater than a 90%reduction (1-log order reduction) in the population of spores ofBacillus cereus or Bacillus subtilis within 10 seconds at 60° C. Incertain embodiments, the sporicidal compositions of the inventionprovide greater than a 99% reduction (2-log order reduction), greaterthan a 99.99% reduction (4-log order reduction), or greater than a99.999% reduction (5-log order reduction) in such population within 10seconds at 60° C.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobistatic composition

The term “substantially similar cleaning performance” refers generallyto achievement by a substitute cleaning product or substitute cleaningsystem of generally the same degree (or at least not a significantlylesser degree) of cleanliness or with generally the same expenditure (orat least not a significantly lesser expenditure) of effort, or both.

As used herein, the term “sulfoperoxycarboxylic acid,” “sulfonatedperacid,” or “sulfonated peroxycarboxylic acid” refers to theperoxycarboxylic acid form of a sulfonated carboxylic acid. In someembodiments, the sulfonated peracids of the present invention aremid-chain sulfonated peracids. As used herein, the term “mid-chainsulfonated peracid” refers to a peracid compound that includes asulfonate group attached to a carbon that is at least one carbon (e.g.,the three position or further) from the carbon of the percarboxylic acidgroup in the carbon backbone of the percarboxylic acid chain, whereinthe at least one carbon is not in the terminal position. As used herein,the term “terminal position,” refers to the carbon on the carbonbackbone chain of a percarboxylic acid that is furthest from thepercarboxyl group.

The term “threshold agent” refers to a compound that inhibitscrystallization of water hardness ions from solution, but that need notform a specific complex with the water hardness ion. Threshold agentsinclude but are not limited to a polyacrylate, a polymethacrylate, anolefin/maleic copolymer, and the like.

As used herein, the term “waters” includes cooling tower waters, foodprocess or transport waters. Cooling tower waters include water beingused in scrubbers, cooling towers and the like, including where water isperforming the function of collecting impurities, capturing productand/or cooling the equipment. Food process or transport waters includeproduce transport waters (e.g., as found in flumes, pipe transports,cutters, slicers, blanchers, retort systems, washers, and the like),belt sprays for food transport lines, boot and hand-wash dip-pans,third-sink rinse waters, and the like. Waters also include domestic andrecreational waters such as pools, spas, recreational flumes and waterslides, fountains, and the like.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods, systems, apparatuses, and compositions of the presentinvention may comprise, consist essentially of, or consist of thecomponents and ingredients of the present invention as well as otheringredients described herein. As used herein, “consisting essentiallyof” means that the methods, systems, apparatuses and compositions mayinclude additional steps, components or ingredients, but only if theadditional steps, components or ingredients do not materially alter thebasic and novel characteristics of the claimed methods, systems,apparatuses, and compositions.

The methods and peroxyformic acid compositions according to theembodiments of the invention present a significant improvement in theprior art and represent a significant change for industries in need ofcleaning and sanitizing products for biofilm. The biofilm remediationmethods and compositions according to the invention obviate the need fornumerous biofilm-reducing agents that are individually and/or incombination unable to completely remove and/or kill biofilm. The biofilmremediation compositions according to the invention provide a superiorbiocidal product, resulting in improved kill rates of biofilm over knownmethods of chemical and biological removal or reduction. This is abeneficial result of the biofilm remediation compositions according tothe invention having a “kill mechanism” capable of penetrating alllayers of a biofilm composition and reaching the substrate surface.These and other benefits of the biofilm remediation methods andcompositions according to the invention will be readily apparent basedon the description contained here, providing improved compositions andmethods for treating ubiquitous biofilm.

Various biofilm-reducing agents are known to provide some beneficialeffects in biofilm reduction and/or prevention. For example, chelatingagents such as EDTA and EGTA, chlorine, iodine and hydrogen peroxidehave previously been used as biofilm-reducing agents. Chelating agentsdestabilize the outer cell membrane of the biofilm. Chlorine, iodine,and hydrogen peroxide remove biofilm by depolymerizing the matrix.Further, biofilm-reducing agents may include antimicrobial proteins,such as nisin, which may be produced by Lactococcus lactus. Biocides orantimicrobial agents are also used as biofilm-reducing agents. Examplesof biocides or antimicrobial agents that are effective include:iodophores; phenols including halo- and nitrophenols and substitutedbisphenols such as 4-hexylresorcinol, 2-benzyl-4-chlorophenol and2,4,4′-trichloro-2′-hydroxydiphenyl ether; quaternary ammonium compoundsand other cationic compounds; cationic surfactants such as alkyl andbenzyl quaternary compounds like N-alkyl (C₁₂-C₁₈) dimethylbenzylammonium chloride monohydrate, dimethyl didecyl ammonium chloride, andN-alkyl and (C₁₂-C₁₄) dimethyl I-napthylmethyl ammonium chloride;organic and inorganic acids and its esters and salts such asdehydroacetic acid, methyl p-hydroxy benzoic acid; aldehydes such asglutaraldehyde; antimicrobial dyes such as is acridines,triphenylmethane dyes and quinones and halogens.

However, as described according to the invention, the peroxyformic acidcompositions and methods described herein provide enhanced antimicrobial“-cidal” mechanisms that are superior over prior biofilm-reducingagents. According to a preferred embodiment, the biofilm remediationcomposition and methods provide up to a 5-log order reduction in thepopulation of microorganisms and pathogens in biofilm, compared to theoptimal 3-log order reduction observed with use of the biofilm-reducingagents described above. The beneficial results of the biofilmremediation composition according to the invention result from thecomposition's penetration of all layers of a biofilm to the substratesurface, providing a complete kill of the microorganisms housed in suchbiofilm.

Methods of Cleaning Industrial Processing Surfaces

The present invention comprises peroxyformic acid compositions which canbe used as a cleaning composition, namely an antimicrobial cleaningcomposition, a booster or as part of an alkaline, acid and/or enzymaticcleaning composition, and methods of use of the same in a periodic CIPapplication. In an exemplary embodiment, the antimicrobial cleaningcompositions or cleaning compositions are particularly suitable for usein scrubbers and cooling towers. As referred to herein, the removing ofmicroorganisms, biofilm, contaminants and other impurities refers to thereduction in microorganisms, biofilm, contaminants and other impuritieson a hard surface within an industrial processing system, thedisbursement of microorganisms, biofilm, contaminants and otherimpurities from such surfaces, and/or the inactivating ofmicroorganisms, biofilm, contaminants and other impurities from suchsurfaces.

In an aspect, the peroxyformic acid compositions are applied to orcontact a hard surface, such as a CO2 scrubber as may be found infermentation systems, such as ethanol and/or breweries, in need ofremoving microbial growth and biofilm. In a further aspect, theperoxyformic acid compositions are applied to or contact a hard surface,such as a cooling tower, in need of removing microbial growth andbiofilm. In a still further aspect, the peroxyformic acid compositionsare applied to or contact a hard surface that has ambient water flowover a substrate (e.g. prone to microbial fouling) in need of removingmicrobial growth and biofilm.

The hard surfaces that can be treated according to the invention includethose designed for periodic cleaning, such as those employed in ethanoland other fermentation applications, cooling towers, scrubbers, drains,sumps, floors, and the like. Exemplary industries that utilize suchsystems include the food industry, the beverage industry, thebiotechnology industry, the pharmaceutical industry, the chemicalindustry, the water purification industry, and the ethanol fermentationindustry. In an aspect, surfaces particularly suited for treatmentaccording to the invention include aqueous cooling systems andscrubbers. Additional suitable surfaces for treatment are disclosed inU.S. Patent Publication Nos. 2014/0263086, 2014/0271418 which areincorporated by reference in its entirety.

In a preferred aspect, the hard surface is a scrubber and/or coolingtower, tower packing materials contained in the scrubber and/or coolingtower, drain, sump, or floor. In certain aspects, the tower and/or mediacontained therein (e.g. packing materials) are contacted with theperoxyformic acid compositions according to the invention. As oneskilled in the art will ascertain various towers for industrialprocessing are packed with material (such as in the CO₂ column) and theongoing flow through thereof water and other chemistry can lead to highmicrobial counts and therefore, the surfaces are in need of treatmentaccording to the invention.

In a depicted embodiment, as shown in FIG. 7 providing a process diagramdepicting an embodiment of the invention a CO₂ industrial scrubber tower12 (including a tower containing various packing material 14) can bedosed with a peroxyformic acid composition 4 (including compositiongenerated onsite from a generator 2), wherein the composition canoptionally be diluted with water 6. The exemplary depicted system is aCO₂ tower, where CO₂ is scrubbed going into the tower 8, and a processwater effluent from the tower 12, along with any exhaust gas 13 are theoutputs of the system.

In other aspects, additional industrial processing surfaces can benefitfrom the treatment with the peroxyformic acid. For example, thetreatment compositions and methods described herein are suitable forvarious once-through, open loop, or closed loop recirculating industrialsystems. Other aqueous systems include, but are not limited to, systemsused in petroleum production and oil recovery (e.g., well casing,transport pipelines, etc.) and refining, geothermal wells, and other oilfield applications; boilers and boiler water systems; systems used inpower generation, mineral process waters including mineral washing,flotation and benefaction; paper mill digesters, washers, bleach plants,white water systems and mill water systems; black liquor evaporators inthe pulp industry; gas scrubbers and air washers; continuous castingprocesses in the metallurgical industry; air conditioning andrefrigeration systems; building fire protection heating water, such aspasteurization water; water reclamation and purification systems;membrane filtration water systems; food processing streams and wastetreatment systems as well as in clarifiers, liquid-solid applications,municipal sewage treatment systems; and industrial or municipal waterdistribution systems.

The methods of treating an industrial processing surface with theperoxyformic acid compositions can include a plurality of steps. A firststep can be referred to as a product removal step or displacement whereproduct (e.g. contaminants and impurities such as aldehydes andalcohols, etc.) is removed from the industrial processing system. Insome aspects, such product can be effectively recovered and used asopposed to discharging as plant effluent. The product removal step canlast as long as it takes to remove and recover product from theindustrial processing system. In general, it is expected that theproduct removal step will take at least a couple minutes for mostsystems.

In a preferred aspect, an on-site and/or in-line generator feeds theperoxyformic acid composition to an industrial processing system. In anaspect, the peroxyformic acid composition is fed into an intake stream,such as a water intake stream, on a periodic basis. In exemplaryembodiment, the peroxyformic acid composition is fed into a water intakestream for about 30 minutes about every 4 hours at a desiredconcentration. In an aspect, from about 25 to about 1,000 ppmperoxyformic acid are dosed to the system, or from about 50 to about 500ppm peroxyformic acid, or still further from about 50 to about 250 ppmperoxyformic acid.

In an aspect of the invention a controller or programmable deviceprovides scheduled dosing and control of other onsite and/or in-linedosing and delivery of water and/or other actives to the system. In suchan aspect a controller is capable of shutting off other chemical feedsat the time of dosing the peroxyformic acid composition. In an exemplaryembodiment, a sufficient amount of time is provided for the industrialprocessing system, such as a scrubber, to be rinsed with only water,including while the peroxyformic acid is being generated. In someembodiments, the amount of time is a few minutes, such as from about 1to about 15 minutes, or about 1 to about 10 minutes, or about 5 minutes.In an embodiment, the peroxyformic acid can be dosed into the water feedline of the processing system, such as the scrubber, turning the feedwater into the peroxyformic acid use solution and treating theprocessing system, such as the scrubber.

In an exemplary dosing interval the peroxyformic acid composition isdosed on an interval suitable to prevent the growth of microbes and theformation of any biofilm. As referred to herein the interval refers tothe amount of time between the dosing of the cleaning compositioncomprising the peroxyformic acid composition. In an exemplaryembodiment, a dosing interval to provide the cleaning composition is atleast once a week. In a further embodiment, a dosing interval to providethe cleaning composition is at least once every other day. In a furtherembodiment, a dosing interval to provide the cleaning composition is atleast a day.

In a preferred exemplary embodiment, a dosing interval for theperoxyformic acid composition is particularly suitable to prevent thegrowth of microbes and the formation of any biofilm, including at aninterval of from about 2 to about 10 hours between dosing, or about 3 toabout 5 hour interval. Without being limited to a particular mechanismof action according to the present invention, in an exemplaryembodiment, a 4 hour dosing interval is suitable based upon the doublingtime of most microbes, preventing a biofilm to get a foothold on asurface. In such an embodiment, after about 30 minutes of peroxyformicacid treatment, the controller shuts off the dosing and/or generating ofthe peroxyformic acid. In an in-line generator embodiment, the shuttingoff of the dosing allows the inert reagents (e.g. formic acid) to clearthe reaction holding line. Thereafter, a chemical supply to theindustrial processing system, such as a scrubber, is turned back on(sodium bisulfite, for example) and can be used in the process of thefacility.

According to an embodiment of the invention for use of the peroxyformicacid in an ethanol fermentation system, bisulfite and most otheradditives would need to be shut off during treatment of the surfaceswith the peroxyformic acid. Without being limited to a particularmechanism of action, the bisulfite would reduce the peroxyformic acidsolution and render it inactive. As a result, in such an embodiment,once the bisulfite stream is turned back on, any residual peroxyformicacid in the system would be eliminated preventing any other downstreameffects of active peroxyformic acid, including for example any residualperoxyformic acid as effluent from the system.

The dosing of the peroxyformic acid compositions for contacting thesurface in need of treatment is for a sufficient amount of time tocontact microorganisms, biofilm and/or other contaminants on thesurface. In an aspect, the peroxyformic acid compositions contacts thesurface for at least about 15 seconds to about 2 hours, for at leastabout 30 seconds to about 1 hour, for at least about 45 seconds to about45 minutes, for at least about 60 seconds to about 30 minutes, or anyrange of time there between.

In an aspect, the peroxyformic acid compositions contact the surface ina use solution of from about 0.001% to about 0.1% active peroxyformicacid, from about 0.005% to about 0.1% active peroxyformic acid, fromabout 0.0075% to about 0.01% active peroxyformic acid, or from about0.0075% to about 0.05% active peroxyformic acid. In a particularlypreferred embodiment, the peroxyformic acid compositions contact thesurface in a use solution of from about 75 ppm active peroxyformic acid(0.0075%).

The peroxyformic acid and the surface can be contacted to form a treatedtarget composition comprising any suitable concentration of saidperoxyformic acid, e.g., at least about 10 ppm, at least about 100 ppm,or preferably from about 10-1,000 ppm of peroxyformic acid. Thecomposition used in the present methods can retain any suitableconcentration or percentage of the peroxyformic acid activity for anysuitable time after the treated target composition is formed. In someembodiments, the composition used in the present methods retains atleast about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initialperoxyformic acid activity for any suitable time after the treatedtarget composition is formed. In other embodiments, the composition usedin the present methods retains at least about 60% of the initialperoxyformic acid activity for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 20, 25, 30 minutes, 1 hour, or 2 hours after thetreated target composition is formed.

In an aspect, the methods of the invention for providing theperoxyformic acid composition to a surface in need of treatment canfurther include an initial step of stopping any flow of CO₂ or otherprocessing component. In a further aspect, the treatment can furtherinclude an initial step of stopping bisulfite source (or other cleaningagent) from contacting the surface. Still further, the treatment caninclude a step of treating the surface in combination with theperoxyformic acid (i.e. co-injected), before the peroxyformic acid,and/or after the peroxyformic acid, with one or more of the followingagents: a defoaming composition, an additional sanitizing agent, anoxidant, and/or a neutralizing composition for any CO₂ on the surface.

In an aspect, the temperature of the surface in need of treatment may bebetween about 2° C. to 60° C., between about 15° C. to 50° C., betweenabout 18° C. to 40° C., or any range of there between. In an aspect, thetemperature of the surface treatment may be ambient temperatures, suchas from 20° C. to 30° C.

Beneficially, the methods of treatment do not negatively interfere withthe compatibility of the systems or a portion of a processing system,and further do not negatively interfere with the process, such asfermentation, as may be measured by the output of the process. In abeneficial aspect the method of treatment does not result in anynegative impact on performance or the effluent from the system. Forexample, in an exemplary embodiment where the peroxyformic acid isemployed in CO₂ scrubbers in a fermentation processing system, theperoxyformic acid does not carry through the fermentation and/ordistillation process in amounts or concentrations. In a still furtherpreferred embodiment, the peroxyformic acid does not cause animalfeeding concerns and/or regulatory concerns by remaining in any productor effluent, such as Dried Distillers Grain (DDG).

The methods of treatment according to the invention provide broadantimicrobial efficacy. In a particular aspects, the methods oftreatment according to the invention provide biofilm antimicrobial andbiocidal efficacy. Exemplary microorganisms susceptible to the peracidcompositions of the invention include, gram positive bacteria (e.g.,Staphylococcus aureus, Bacillus species (sp.) like Bacillus subtilis,Clostridia sp.), gram negative bacteria (e.g., Escherichia coli,Pseudomonas sp., Klebsiella pneumoniae, Legionella pneumophila,Enterobacter sp., Serratia sp., Desulfovibrio sp., and Desulfotomaculumsp.), yeasts (e.g., Saccharomyces cerevisiae and Candida albicans),molds (e.g., Aspergillus niger, Cephalosporium acremonium, Penicilliumnotatum, and Aureobasidium pullulans), filamentous fungi (e.g.,Aspergillus niger and Cladosporium resinae), algae (e.g., Chlorellavulgaris, Euglena gracilis, and Selenastrum capricornutum), and otheranalogous microorganisms and unicellular organisms (e.g., phytoplanktonand protozoa). Other exemplary microorganisms susceptible to the peracidcompositions of the invention include the exemplary microorganismsdisclosed in U.S. patent application US 2010/0160449, e.g., the sulfur-or sulfate-reducing bacteria, such as Desulfovibrio and Desulfotomaculumspecies.

The methods of treatment according to the invention provide othercontaminant removal, such as mineral scale removal and removal ofmineral buildup conventionally found on hard surfaces employed inindustrial processing. In a particular aspects, the methods of treatmentaccording to the invention provide scale and mineral removal andprevention of buildup or accumulation. Mineral scales are soluble saltsthat precipitate out as crystalline mineral scales within a system, suchas fermentation, filtration and other industrial processing systems.Examples of mineral scales include calcium carbonate, calcium sulfate,calcium phosphate, barium sulfate, strontium sulfate, iron hydroxide,silicone dioxide (silica), calcium oxalate, etc.

In an aspect, the methods of treatment with the peroxyformic acidcompositions can further comprise additional treatment cycles selectedfrom an acidic treatment, an alkaline treatment, an enzymatic treatmentand/or a neutral treatment either before or after the peroxyformic acidcomposition contacts the surface. Another step often used can bereferred to as a pre-rinse step. In general, water and/or an alkalinesolution can be run through the processing system to remove soils.

In an aspect, an alkaline treatment employs an alkaline use solution tocontact the surface at the same time, and/or before, and/or after theperoxyformic acid composition has been applied to the surface. Exemplaryalkaline sources suitable for use with the methods of the presentinvention include, but are not limited to, basic salts, amines, alkanolamines, carbonates and silicates. Other exemplary alkaline sources foruse with the methods of the present invention include NaOH (sodiumhydroxide), KOH (potassium hydroxide), TEA (triethanol amine), DEA(diethanol amine), MEA (monoethanolamine), sodium carbonate, andmorpholine, sodium metasilicate and potassium silicate. The alkalinesource selected is compatible with the surface to be cleaned. In someembodiments, the alkaline override use solution includes an activatorcomplex. In other embodiments, an activator complex is applied to thesurface prior to the application of an alkaline override use solution.The alkaline override use solution selected is dependent on a variety offactors, including, but not limited to, the type of soil to be removed,and the surface from which the soil is removed. In some embodiments, thepH of the alkaline override use solution is about 10 to about 13. Insome embodiments, the pH is about 12. The pH of the alkaline overrideuse solution is formulated to facilitate soil removal from the selectedsurface, while also being compatible with the selected surface. In someembodiments, the pH of the total solution used to clean the surface,i.e., the pH of the solution after both the active oxygen use solutionand the alkaline override use solutions have been applied to thesurface, is about 10 to about 11.5.

In an aspect, an acidic treatment employs an acidic use solution tocontact the surface at the same time, and/or before, and/or after theperoxyformic acid composition has been applied to the surface. Exemplaryacid sources suitable for use with the methods of the present inventioninclude, but are not limited to, mineral acids (e.g., phosphoric acid,nitric acid, sulfuric acid) and organic acids (e.g., lactic acid, aceticacid, hydroxyacetic acid, citric acid, glutamic acid, glutaric acid,methane sulfonic acid, acid phosphonates (e.g., HEDP), and gluconicacid). In some embodiments, the ideal additional acidic componentprovides good chelation once neutralized by the alkaline override usesolution. In some embodiments, the additional acidic component presentin the active oxygen use solution includes a carboxylic acid. Generally,carboxylic acids have the formula R—COOH wherein the R may represent anynumber of different groups including aliphatic groups, alicyclic groups,aromatic groups, heterocyclic groups, all of which may be saturated orunsaturated as well as substituted or unsubstituted. Carboxylic acidsfor use with the methods of the present invention may include thosehaving one, two, three, or more carboxyl groups.

Cleaning Compositions

In one aspect, the present invention employs peroxyformic acidcompositions which may be dosed at a point of use and/or generated insitu at a point of use for the treatment according to the invention. Asreferred to herein, the peroxyformic acid compositions comprisesperoxyformic acid in an suitable type of aqueous composition. Forexample, the aqueous composition can be an aqueous solution. In anotherexample, the resulting aqueous composition can be an aqueous suspension.The peroxyformic acid compositions can include a range of concentrationsof the peracid (w/w) and the hydrogen peroxide (w/w), including at leastabout 2 to about 1,500, e.g., about 2, 3, 4, 5, 6, 7, 8, 9, 10, orgreater.

The peroxyformic acid compositions can include any suitableconcentration of hydrogen peroxide, including about 5% (w/w) or lesshydrogen peroxide, e.g., about 5% (w/w), 4.5% (w/w), 4% (w/w), 3.5%(w/w), 3% (w/w), 2.5% (w/w), 2% (w/w), 1.5% (w/w), or 1% (w/w) or lesshydrogen peroxide.

The peroxyformic acid compositions can include any suitableconcentration of peroxyformic acid. In some embodiments, the resultingaqueous composition comprises from about 0.001% (w/w) to about 20% (w/w)peroxyformic acid, e.g., about 0.001%-0.005% (w/w), 0.005%-0.01% (w/w),0.01%-0.05% (w/w), 0.05%-0.1% (w/w), 0.1%-0.5% (w/w), 0.5%-1% (w/w),1%-2% (w/w), 2%-3% (w/w), 3%-4% (w/w), 4%-5% (w/w), 5%-6% (w/w), 6%-7%(w/w), 7%-8% (w/w), 8%-9% (w/w), 9%-10% (w/w), 10%-11% (w/w), 11%-12%(w/w) 12%-13% (w/w) 13%-14% (w/w) 14%-15% (w/w) 15%-16% (w/w) 16%-17%(w/w) 17%-18% (w/w) 18%-19% (w/w) 19%-20% (w/w) peroxyformic acid.

The peroxyformic acid compositions according to the invention cancomprise a stabilizing agent. Any suitable stabilizing agents can beused. Exemplary stabilizing agents include a phosphonate salt(s) and/ora heterocyclic dicarboxylic acid, e.g., dipicolinic acid. In an aspect,the compositions and/or methods can further comprise using a stabilizingagent for peroxyformic acid, a stabilizing agent for hydrogen peroxide,and/or a pH buffering agent. The present methods can use any suitablestabilizing agent. Exemplary stabilizing agents include a phosphonatesalt(s) and/or a heterocyclic dicarboxylic acid, e.g., dipicolinic acid.In some embodiments, the stabilizing agent is pyridine carboxylic acidbased stabilizers, such as picolinic acid and salts,pyridine-2,6-dicarboxylic acid and salts, and phosphonate basedstabilizers, such as phosphoric acid and salts, pyrophosphoric acid andsalts and most commonly 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)and salts. In other embodiments, the present methods can use two or morestabilizing agents, e.g., HEDP and 2,6-pyridinedicarboxylic acid (DPA).

In Situ Generated Peroxyformic Acid

Any of the present methods of generating the peroxyformic acid can beconducted at any suitable temperature. In some embodiments, the presentmethods can be conducted at a temperature ranging from about −2° C. toabout 70° C., about 10° C. to about 70° C., e.g., about 10° C.-15° C.,15° C.-20° C., 20° C.-25° C., 25° C.-30° C., 30° C.-35° C., 35° C.-40°C., 40° C.-45° C., 45° C.-50° C., 50° C.-55° C., 55° C.-60° C., 60°C.-65° C., or 65° C.-70° C. In other embodiments, the present methodscan be conducted under ambient conditions. In still other embodiments,the present methods can be conducted under heating, e.g., at atemperature ranging from about 30° C.-35° C., 35° C.-40° C., 40° C.-45°C., 45° C.-50° C., 50° C.-55° C., 55° C.-60° C., 60° C.-65° C., or 65°C.-70° C.

The present methods of generating the peroxyformic acid can be conductedin the presence of a catalyst. Any suitable catalyst can be used in thepresent methods. In some embodiments, the catalyst can be a mineralacid, e.g., sulfuric acid, methanesulfonic acid, nitric acid, phosphoricacid, pyrophosphoric acid, polyphosphoric acid or phosphonic acid.

The present methods of generating the peroxyformic acid can be conductedin the presence of a cation acid exchange resin system. Any suitablecation acid exchange resin system can be used in the present methods. Insome embodiments, the cation acid exchange resin system is a strongcation acid exchange resin system. In other embodiments, the acidexchange resin system is sulfonic acid exchange resin, e.g.,commercially-available as Dowex M-31 or Nafion.

The resulting aqueous peroxyformic acid composition can comprise astabilizing agent for the peracid. Any suitable stabilizing agents canbe used in the present methods. Exemplary stabilizing agents include aphosphonate salt(s) and/or a heterocyclic dicarboxylic acid, e.g.,dipicolinic acid.

The present methods can further comprise a step of reducing theconcentration of the hydrogen peroxide in the resulting aqueouscomposition. The concentration of the hydrogen peroxide in the resultingaqueous composition can be reduced using any suitable methods. Forexample, the concentration of the hydrogen peroxide in the resultingaqueous composition can be reduced using a catalase or a peroxidase.

The present methods can be used to generate peroxyformic acid in anysuitable manner or at any suitable location. In some embodiments, thepresent methods can be used to generate peroxyformic acid in situ forthe application of the formed peroxyformic acid. Exemplary peracidforming compositions including use of an organic acid and an oxidizingagent, such as hydrogen peroxide may be employed to generate a peracidcomposition in situ. Description of exemplary in situ methods forperacid forming compositions is provided in U.S. Pat. Nos. 8,846,107 and8,877,254, which are herein incorporated by reference in their entirety.

Controllers and Onsite Generators

In an embodiment of the invention, an in-line peroxyformic acidgenerator is provided on site to feed peroxyformic acid into a waterintake stream on a scheduled basis according to the methods of use. Inan aspect, a scheduled dosing of 30 minutes every 4 hours at 75 ppmactive peroxyformic acid provides a desired result of preventing biofilmin various industrial processing systems according to the invention. Inan aspect, controller capable of timing the dose is responsible forshutting off other chemical feeds at the time of dosing, allowing asufficient time for the surface (e.g. scrubber) to rinse with onlywater, while the peroxyformic acid is being generated (e.g. 5 minutes),then dosing into the water feed line of the surface (e.g. scrubber),turning the feed water into the peroxyformic acid use solution andtreating the surface. After the period of peroxyformic acid treatment,e.g. 30 minutes, the controller would shut off the generator, allow theinert acid, e.g. formic acid, to clear the reaction holding line, shutdown the reactor, and turn the chemical supply back on (e.g. sodiumbisulfite) used in the process of the facility. As one skilled in theart will ascertain, bisulfite and most other additives would need to beshut off during treatment as they would reduce the peroxyformic acidsolution and render it inactive. Once the bisulfite stream is turnedback on, any residual peroxyformic acid in the system would beeliminated preventing any other downstream effects of activeperoxyformic acid.

In certain aspects, the in-line peroxyformic acid generator may includea monitoring and controlling unit that comprises a controller device anda plurality of sensors. Each of the plurality of sensors may beconfigured to obtain a different characteristic of the chemical feedsand each sensor may also be in communication with the controller. Theplurality of sensors can comprise, for example, sensors for measuringconductivity, concentration, pH, oxidation/reduction potential (ORP),fluorescence (or other monitoring visual indicator), biocideconcentration, turbidity, temperature, flow, dissolved oxygen (DO), andthe like.

Based on signals received from the sensors, the controller may sendsignals to chemical injection pumps, which are in fluid communicationwith various chemical feeds, to turn the pumps off (cause them to stopadding chemical) or turn them on (cause them to add a specified amountof more chemical). The components of this automated system may be incommunication with each other in any number of ways, including throughany combination of wired connection, a wireless connection,electronically, cellularly, through infrared, satellite, or according toany other types of communication networks, topologies, protocols, andstandards.

As used herein, the term “controller” or “controller device” refers to amanual operator or an electronic device having components such as aprocessor, memory device, digital storage medium, a communicationinterface including communication circuitry operable to supportcommunications across any number of communication protocols and/ornetworks, a user interface (e.g., a graphical user interface that mayinclude cathode ray tube, liquid crystal display, plasma display, touchscreen, or other monitor), and/or other components. The controller ispreferably operable for integration with one or moreapplication-specific integrated circuits, programs, computer-executableinstructions or algorithms, one or more hard-wired devices, wirelessdevices, and/or one or more mechanical devices. Moreover, the controlleris operable to integrate the feedback, feed-forward, or predictiveloop(s) of the invention. Some or all of the controller system functionsmay be at a central location, such as a network server, forcommunication over a local area network, wide area network, wirelessnetwork, internet connection, microwave link, infrared link, wirednetwork (e.g., Ethernet) and the like. In addition, other componentssuch as a signal conditioner or system monitor may be included tofacilitate signal transmission and signal-processing algorithms.

The disclosed monitoring and controlling system provides methods togenerate real-time, on-line, reliable data from the water of theindustrial system. Based upon the data received by the controller fromthe plurality of sensors, real-time adjustments can be made to thewater. For example, the plurality of sensors may provide continuous orintermittent feedback, feed-forward, or predictive information to thecontroller, which can relay this information to a relay device, such asthe Nalco Global Gateway, which can transmit the information viacellular communications to a remote device, such as a cellulartelephone, computer, or any other device that can receive cellularcommunications. This remote device can interpret the information andautomatically send a signal (e.g. electronic instructions) back, throughthe relay device, to the controller to cause the controller to makecertain adjustments to the output of the chemical injection pumps. Theinformation may also be processed internally by the controller and thecontroller can automatically send signals to the pumps, to adjust theamount of chemical injection. Based upon the information received by thecontroller from the plurality of sensors or from the remote device, thecontroller can transmit signals to the various pumps to make automatic,real-time adjustments, to the amount of chemical that the pumps areinjecting into the water of the system.

In certain aspects, the remote device or controller can includeappropriate software to receive data from the plurality of sensors anddetermine if the data indicates that one or more measured properties ofthe water are within, or outside, an acceptable range. The software canalso allow the controller or remote device to determine appropriateactions that should be taken to remedy the property that is outside ofthe acceptable range. The monitoring and controlling system and/orcontroller disclosed herein can incorporate programming logic to convertanalyzer signals from the plurality of sensors to pump adjustment logicand, in certain embodiments, control one or more of a plurality ofchemical injection pumps with a unique basis.

Data transmission of measured properties or signals to chemical pumps,alarms, remote monitoring devices, such as computers or cellulartelephones, or other system components is accomplished using anysuitable device, and across any number of wired and/or wirelessnetworks, including as examples, WiFi, WiMAX, Ethernet, cable, digitalsubscriber line, Bluetooth, cellular technologies, etc. The Nalco GlobalGateway is an example of a suitable device. Any suitable interfacestandard(s), such as an Ethernet interface, wireless interface (e.g.,IEEE 802.11a/b/g/x, 802.16, Bluetooth, optical, infrared,radiofrequency, etc.), universal serial bus, telephone network, thelike, and combinations of such interfaces/connections may be used. Asused herein, the term “network” encompasses all of these datatransmission methods. Any of the described devices (e.g., archivingsystems, data analysis stations, data capturing devices, processdevices, remote monitoring devices, chemical injection pumps, etc.) maybe connected to one another using the above-described or other suitableinterface or connection.

Formic Acid and Hydrogen Peroxide

In an aspect, peroxyformic acid compositions generated in situ comprisecontacting formic acid with hydrogen peroxide to form a resultingaqueous composition that comprises a peracid that comprises peroxyformicacid. Additional disclosure of suitable in situ reaction for thegeneration of peroxyformic acid is disclosed in application Ser. No.14/972,308, titled Methods for Forming Peroxyformic Acid and UsesThereof, which is herein incorporated by reference in its entirety.

In an aspect, before said contacting, the ratio between theconcentration of said formic acid (w/v) and the concentration of saidhydrogen peroxide (w/v) is about 2 or higher, and the ratio between theconcentration of said peracid (w/w) and the concentration of hydrogenperoxide (w/w) in said formed resulting aqueous composition reachesabout 2 or higher within preferably about 1 hour, or preferably withinabout 10 minutes of said contacting.

The formic acid used in the present methods can be provided in anysuitable way. In some embodiments, before the contacting step, theformic acid can be provided in a composition that comprises formic acid,e.g., an aqueous solution that comprises formic acid. In otherembodiments, before the contacting step, the formic acid can be providedin a composition that comprises a substance that generates formic acidupon contact with an aqueous composition. Any suitable substance thatgenerates formic acid can be used in the present methods. The substancecan be a salt of formate, e.g., a sodium or ammonium salt of formate, oran ester of formate. Exemplary esters of formate include glycerolformates, pentaerythritol formates, mannitol formates, propylene glycolformates, sorbitol formates and sugar formates. Exemplary sugar formatesinclude sucrose formates, dextrin formates, maltodextrin formates, andstarch formates. In some embodiments the formates may be provided in asolid composition, such as a starch formate.

The hydrogen peroxide used in the present methods can be provided in anysuitable way. In some embodiments, before the contacting step, thehydrogen peroxide can be provided in a composition that compriseshydrogen peroxide, e.g., an aqueous solution that comprises hydrogenperoxide. In other embodiments, before the contacting step, the hydrogenperoxide can be provided in a composition that comprises a substancethat generates hydrogen peroxide upon contact with an aqueouscomposition. Any suitable substance that generates hydrogen peroxide canbe sued in the present methods. The substance can comprise a precursorof hydrogen peroxide. Any suitable precursor of hydrogen peroxide can beused in the present methods. For example, the precursor of hydrogenperoxide can be sodium percarbonate, sodium perborate, urea hydrogenperoxide, or PVP-hydrogen peroxide.

In some embodiments, formic acid provided in a first aqueous compositionis contacted with hydrogen peroxide provided in a second aqueouscomposition to form peroxyformic acid in the resulting aqueouscomposition. In other embodiments, formic acid provided in a firstaqueous composition is contacted with a substance that generateshydrogen peroxide upon contact with an aqueous composition provided in asecond solid composition to form peroxyformic acid in the resultingaqueous composition. In still other embodiments, a substance thatgenerates formic acid upon contact with an aqueous composition providedin a first solid composition is contacted with hydrogen peroxideprovided in a second aqueous composition to form peroxyformic acid inthe resulting aqueous composition. In yet other embodiments, a substancethat generates formic acid upon contact with an aqueous compositionprovided in a first solid composition and a substance that generateshydrogen peroxide upon contact with an aqueous composition provided in asecond solid composition are contacted with a third aqueous compositionto form peroxyformic acid in the resulting aqueous composition. In yetother embodiments, a substance that generates formic acid upon contactwith an aqueous composition and a substance that generates hydrogenperoxide upon contact with an aqueous composition are provided in afirst solid composition, and the first solid composition is contactedwith a second aqueous composition to form peroxyformic acid in theresulting aqueous composition.

The resulting aqueous composition that comprises peroxyformic acid canbe any suitable types of aqueous compositions. For example, theresulting aqueous composition can be an aqueous solution. In anotherexample, the resulting aqueous composition can be an aqueous suspension.

Before the contacting step, the ratio between the concentration of theformic acid (w/v) and the concentration of the hydrogen peroxide (w/v)can be in any suitable range. In some embodiments, before thecontacting, the ratio between the concentration of the formic acid (w/v)and the concentration of the hydrogen peroxide (w/v) can be from about 2to about 100, e.g., about 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10,10-15, 15-20, 20-25, 25-30, 30-35, 35-40, 40-45 or 45-50 or greater fromabout 50-100.

The ratio between the concentration of the peracid (w/w) and theconcentration of hydrogen peroxide (w/w) in the formed aqueouscomposition can reach any suitable range. In some embodiments, the ratiobetween the concentration of the peracid (w/w) and the concentration ofhydrogen peroxide (w/w) in the formed aqueous composition can reach,within about 4 hours, or preferably 2 hours of the contacting, fromabout 2 to about 1,500, e.g., about 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9,9-10, 10-15, 15-20, 20-25, 25-30, 30-35, 35-40, 40-45, 45-50, 50-60,60-70, 70-80, 80-90, 90-100, 100-200, 200-300, 300-400, 400-500,500-600, 600-700, 700-800, 800-900, 900-1,000, 1,000-1,100, 1,100-1,200,1,200-1,300, 1,300-1,400, or 1,400-1,500. In other embodiments, theratio between the concentration of the peracid (w/w) and theconcentration of hydrogen peroxide (w/w) in the formed aqueouscomposition reaches at least about 10 within about 30 minutes of thecontacting, preferably at least about 10-40 within about 30 minutes ofthe contacting.

The formed aqueous composition can comprise any suitable concentrationof hydrogen peroxide. In some embodiments, the formed aqueouscomposition can comprise about 5% (w/w) or less hydrogen peroxide, e.g.,about 5% (w/w), 4.5% (w/w), 4% (w/w), 3.5% (w/w), 3% (w/w), 2.5% (w/w),2% (w/w), 1.5% (w/w), 1% (w/w), 0.9% (w/w), 0.8% (w/w), 0.7% (w/w), 0.6%(w/w), 0.5% (w/w), 0.4% (w/w), 0.3% (w/w), 0.2% (w/w), 0.1% (w/w), 0.05%(w/w), 0.01% (w/w), 0.005% (w/w), or 0.001% (w/w) of hydrogen peroxide.In other embodiments, the formed aqueous composition reaches about 2%(w/w) or less hydrogen peroxide within about 1 hour, or preferablywithin about 10 minutes of the contacting. In still other embodiments,the formed aqueous composition reaches about 1% (w/w) or less hydrogenperoxide within about 1 hour of the contacting. In yet otherembodiments, the formed aqueous composition reaches about 0% (w/w) toabout 0.001% (w/w) hydrogen peroxide and maintains about 0% (w/w) toabout 0.001% (w/w) hydrogen peroxide for about 1 hour.

The resulting aqueous composition can comprise any suitableconcentration of peroxyformic acid. In some embodiments, the resultingaqueous composition comprises from about 0.001% (w/w) to about 20% (w/w)peroxyformic acid, e.g., about 0.001%-0.005% (w/w), 0.005%-0.01% (w/w),0.01%-0.05% (w/w), 0.05%-0.1% (w/w), 0.1%-0.5% (w/w), 0.5%-1% (w/w),1%-2% (w/w), 2%-3% (w/w), 3%-4% (w/w), 4%-5% (w/w), 5%-6% (w/w), 6%-7%(w/w), 7%-8% (w/w), 8%-9% (w/w), 9%-10% (w/w), 10%-11% (w/w), 11%-12%(w/w) 12%-13% (w/w) 13%-14% (w/w) 14%-15% (w/w) 15%-16% (w/w) 16%-17%(w/w) 17%-18% (w/w) 18%-19% (w/w) 19%-20% (w/w) peroxyformic acid.

The formic acid and the hydrogen peroxide can be contacted in theabsence of a C₂-C₂₂ carboxylic acid and/or a C₂-C₂₂ percarboxylic acidand the peracid in the formed aqueous composition comprises peroxyformicacid only.

The formic acid and hydrogen peroxide can be contacted in the presenceof a C₂-C₂₂ carboxylic acid and the peracid in the formed aqueouscomposition comprises peroxyformic acid and the C₂-C₂₂ percarboxylicacid. Any suitable C₂-C₂₂ carboxylic acid can be used in the presentmethods. In some embodiments, the C₂-C₂₂ carboxylic acid is acetic acid,octanoic acid and/or sulfonated oleic acid, and the peracid in theformed aqueous composition comprises peroxyformic acid and one or moreof peroxyacetic acid, peroxyoctanoic acid and peroxysulfonated oleicacid.

The formic acid provided in a first aqueous composition can be contactedwith the hydrogen peroxide provided in a second aqueous composition thatalso comprises peroxyacetic acid to form a resulting aqueous compositionthat comprises a total peracid that comprises peroxyformic acid andperoxyacetic acid. Before the contacting step, the ratio between theconcentration of the formic acid (w/v) and the concentration of thehydrogen peroxide (w/v) can be at any suitable range. The ratio betweenthe concentration of total peracid (w/w) and the concentration ofhydrogen peroxide (w/w) in the resulting aqueous composition can alsoreach any suitable range. In some embodiments, before the contacting,the ratio between the concentration of the formic acid (w/v) and theconcentration of the hydrogen peroxide (w/v) can be about 5 or higherand the ratio between the concentration of total peracid (w/w) and theconcentration of hydrogen peroxide (w/w) in the resulting aqueouscomposition reaches at least about 5 within about 2 minutes of thecontacting. In other embodiments, the ratio between the concentration oftotal peracid (w/w) and the concentration of hydrogen peroxide (w/w) inthe resulting aqueous composition can reach at least about 10 withinabout 20 minutes of the contacting. In yet other embodiments, before thecontacting, the ratio between the concentration of the formic acid (w/v)and the concentration of the hydrogen peroxide (w/v) can be about 20 orhigher and the ratio between the concentration of total peracid (w/w)and the concentration of hydrogen peroxide (w/w) in the resultingaqueous composition can reach at least about 10 within at least about 1minute of the contacting. The concentration of hydrogen peroxide (w/w)in the resulting aqueous composition can reach any suitableconcentration. In some embodiments, the concentration of hydrogenperoxide (w/w) in the resulting aqueous composition can reach about 0%(w/w) to about 0.001% (w/w) hydrogen peroxide within at least about 4hours, or preferably 2 hours of the contacting. In other embodiments,the concentration of hydrogen peroxide (w/w) in the resulting aqueouscomposition can remain at about 0% (w/w) to about 0.001% (w/w) for least1 hour.

Esters and Hydrogen Peroxide

In an aspect, peroxyformic acid compositions generated in situ comprisecontacting an ester of a polyhydric alcohol and formic acid and hydrogenperoxide or a substance that generates hydrogen peroxide when in contactwith a liquid to form a resulting aqueous composition that comprises aperacid that comprises peroxyformic acid. Additional disclosure ofsuitable in situ reaction for the generation of peroxyformic acid isdisclosed in application Ser. No. 14/973,389, titled Generation ofPeroxyformic Acid Through Polyhydric Alcohol Formate, which is hereinincorporated by reference in its entirety.

In one aspect, the present invention is directed to a peroxyformic acidforming composition comprising: a) a first reagent that comprises anester of a polyhydric alcohol and formic acid, and b) a second reagentthat comprises hydrogen peroxide or that comprises a substance thatgenerates hydrogen peroxide when in contact with a liquid, wherein 1)said first reagent and said second reagent are kept separately prior touse, and when it is time to generate peroxyformic acid, said firstreagent and said second reagent are configured to be contacted with eachother to form a liquid that comprises peroxyformic acid and has a pHbelow about 11, and pH of the formed liquid becomes about 8 or lowerwithin about 1 minute after the contact between said first reagent andsaid second reagent; or 2) said second reagent comprises a substancethat generates hydrogen peroxide when in contact with a liquid, saidfirst reagent and said second reagent are comprised in a solidcomposition, and when it is time to generate peroxyformic acid, saidsolid composition is configured to be contacted with a liquid to form aliquid that comprises peroxyformic acid and has a pH below about 11, andpH of the formed liquid becomes about 8 or lower within about 1 minuteafter the contact between said solid composition and said liquid.

In some embodiments, the present peroxyformic acid forming compositioncomprises a) a first reagent that comprises an ester of a polyhydricalcohol and formic acid, and b) a second reagent that comprises hydrogenperoxide or that comprises a substance that generates hydrogen peroxidewhen in contact with a liquid, wherein said first reagent and saidsecond reagent are kept separately prior to use, and when it is time togenerate peroxyformic acid, said first reagent and said second reagentare configured to be contacted with each other to form a liquid thatcomprises peroxyformic acid and has a pH below about 11, and pH of theformed liquid becomes about 8 or lower within about 1 minute after thecontact between said first reagent and said second reagent. In otherembodiments, the present peroxyformic acid forming composition comprisesa) a first reagent that comprises an ester of a polyhydric alcohol andformic acid, and b) a second reagent that comprises a substance thatgenerates hydrogen peroxide when in contact with a liquid, wherein saidfirst reagent and said second reagent are comprised in a solidcomposition, and when it is time to generate peroxyformic acid, saidsolid composition is configured to be contacted with a liquid to form aliquid that comprises peroxyformic acid and has a pH below about 11, andpH of the formed liquid becomes about 8 or lower within about 1 minuteafter the contact between said solid composition and said liquid.

The present peroxyformic acid forming compositions can comprise anysuitable ester of a polyhydric alcohol and formic acid. Typically, apolyhydric alcohol refers to a molecule with two or more hydroxyl (—OH)groups. An ester of a polyhydric alcohol and formic acid refers to anester formed between a polyhydric alcohol and formic acid. Esters asreferred to herein are considered ‘water-less’ systems as no additionalwater is added to the reaction. In some embodiments, the presentperoxyformic acid forming compositions comprise glycerol formates,pentaerythritol formates, mannitol formates, propylene glycol formates,sorbitol formates and sugar formates. The present peroxyformic acidforming compositions can comprise any suitable sugar formates, e.g.,sucrose formates, dextrin formates, maltodextrin formates, or starchformates.

In a preferred embodiment, a liquid reaction employs glycerol formates,pentaerythritol formates, mannitol formates, or propylene glycolformates. In a still further preferred embodiment, a liquid reactionemploys glycerol formates. Beneficially, the glycerol formates rapidlyundergo hydrolysis for peroxyformic acid generation according to themethods of the invention. In an aspect, the precursors provided do notinclude additional water added into the system which would negativelyinterfere with the kinetics of the reaction between the ester of apolyhydric alcohol and formic acid and hydrogen peroxide. In an aspect,the premixes and the peroxyformic acid forming composition do not addfree water into the systems, which would negatively interfere with theester, e.g. glycerol formates.

In a preferred embodiment, a solid reaction employs sugar formates e.g.,sucrose formates, dextrin formates, maltodextrin formates, or starchformates. In a still further preferred embodiment, a solid reactionemploys starch formates.

The present peroxyformic acid forming compositions can comprise a usesolution or a concentrate of the ester of a polyhydric alcohol andformic acid. In some aspects, the methods of the invention generate aperoxyformic acid through a concentrate reaction of the ester of apolyhydric alcohol and formic acid. In other aspects, the methods of theinvention generate a peroxyformic acid through a diluted use solutionreaction of the ester of a polyhydric alcohol and formic acid.

The first or second reagent can have any suitable pH range in thepresent peroxyformic acid forming compositions. For example, the firstor second reagent can have a pH below about 11, or from about −2 toabout 11, or from about 0 to about 11, e.g., about −2 to about −1, −2 toabout 0, 0-1, 0-2, 0-3, 0-4, 0-5, 0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2,1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7,2-8, 2-9, 2-10, 2-11, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5,4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7,6-8, 6-9, 6-10, 6-11, 6-7, 7-8, 7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10,9-11, 10-11, or at about −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.In some embodiments, the first or second reagent has a pH ranging fromabout 5 to about 10, e.g., about 5-6, 5-7, 5-8, 5-9, 5-10, 6-7, 6-8,6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10, or 9-10. In other embodiments, thefirst or second reagent has a pH at about 9.

The first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises peroxyformic acid and has any suitable pH, including a pHbelow about 11, or from about −2 to about 11, or from about 0 to about11, e.g., about −2 to about −1, −2 to about 0, 0-1, 0-2, 0-3, 0-4, 0-5,0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9,1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 3-4, 3-5,3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11,5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9, 6-10, 6-11, 6-7, 7-8,7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11, 10-11, or at about −2, −1,0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. In some embodiments, the firstreagent and the second reagent are configured to be contacted with eachother to form a liquid, e.g., a solution, that comprises peroxyformicacid and has a pH ranging from about −2 to about 11, 0 to about 10, or 5to about 10, e.g., about −2-0, 0-1, 1-2, 2-3, 3-4, 4-5, 5-6, 5-7, 5-8,5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10, 9-10, or10-11. In other embodiments, the first reagent and the second reagentare configured to be contacted with each other to form a liquid, e.g., asolution, that comprises peroxyformic acid and has a pH at about 9. In apreferred aspect, the formed liquid, e.g., a solution, that comprisesperoxyformic acid and has a pH near neutral, from about 6-7.

The pH of the formed liquid can become about 8 or lower within about 1minute after the contact between the first reagent and the secondreagent or after the contact between the solid composition and theliquid. In some embodiments, the pH of the formed liquid can becomeabout 8 or lower within about 1 second, 2 seconds, 3 seconds, 4 seconds,5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds after the contact betweenthe first reagent and the second reagent or after the contact betweenthe solid composition and the liquid. In other embodiments, the pH ofthe formed liquid comprising peroxyformic acid becomes about 8 or lowerwithin about 1 minute or less. In an aspect, the pH of the formed liquidcomprising peroxyformic acid becomes about 8 or lower within about 45seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds orless, 25 seconds or less, 20 seconds or less, 15 seconds or less, 10seconds or less, or 5 seconds or less. In an aspect, the pH of theformed liquid comprising peroxyformic acid becomes about 8 or lower nearinstantaneously. In other embodiments, the pH of the formed liquid canbecome about lower than −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, or 8 withinabout 1 minute after the contact between the first reagent and thesecond reagent or after the contact between the solid composition andthe liquid.

The liquid that comprises peroxyformic acid can maintain the pH rangingfrom about −2 to about 8, or from about 0 to about 8 for any suitabletime after the contact between the first reagent and the second reagent,or after the contact between the composition and a liquid. In someembodiments, the liquid that comprises peroxyformic acid maintains thepH ranging from about −2 to about 8, or from about 0 to about 8 fromabout 1 second to about 10 hours after the contact between the firstreagent and the second reagent or after the contact between thecomposition and a liquid. For example, the liquid that comprisesperoxyformic acid can maintain the pH at about −2, −1, 0, 1, 2, 3, 4, 5,6, 7, or 8 from about 1 second to about 10 hours after the contactbetween the first reagent and the second reagent or after the contactbetween the composition and a liquid. In another example, the liquidthat comprises peroxyformic acid can maintain the pH ranging from about0 to about 8 for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9hours, or 10 hours. In a preferred aspect, the formed liquid, e.g., asolution, that comprises peroxyformic acid and has a pH near neutral,from about 6-7 in a use solution.

In some embodiments, the first reagent and the second reagent areconfigured to be contacted with each other to form a solution thatcomprises peroxyformic acid and has a pH ranging from about 4 to about 8or 9, e.g., about 4-5, 5-6, 6-7, 7-8, or 8-9. In a preferred aspect, theformed liquid, e.g., a solution, that comprises peroxyformic acid andhas a pH near neutral, from about 6-7 in a use solution. In one example,the first reagent and the second reagent are configured to be contactedwith each other to form a solution that comprises peroxyformic acid andhas a pH ranging from about 6 to about 8 or 9. The first reagent and thesecond reagent can be configured to be contacted with each other to forma solution that comprises peroxyformic acid and has a pH ranging fromabout 4 to about 8 or 9, and the solution can maintain the pH range forany suitable amount of time, e.g., from about 1 minute to about 24hours. For example, the solution can maintain the pH range from about 4to about 8 or 9 for at least about 1 minute, 2 minutes, 3 minutes, 4minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or10 hours.

In other embodiments, the solid composition is configured to becontacted with a liquid to form a solution that comprises peroxyformicacid and has a pH ranging from about 4 to about 8 or 9, e.g., about 4-5,5-6, 6-7, 7-8, or 8-9. In one example, the solid composition isconfigured to be contacted with a liquid to form a solution thatcomprises peroxyformic acid and has a pH ranging from about 6 to about 8or 9. The solid composition is configured to be contacted with a liquidto form a solution that comprises peroxyformic acid and has a pH rangingfrom about 4 to about 8 or 9, and the solution can maintain the pH rangefor any suitable amount of time, e.g., from about 1 minute to about 24hours. For example, the solution can maintain the pH range from about 4to about 8 or 9 for at least about 1 minute, 2 minutes, 3 minutes, 4minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or10 hours. In a preferred aspect, the formed liquid, e.g., a solution,that comprises peroxyformic acid and has a pH near neutral, from about6-7 in a use solution.

The first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises peroxyformic acid under any suitable conditions ortemperature. In some embodiments, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises peroxyformic acid under ambientconditions. In other embodiments, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises peroxyformic acid at a temperatureranging from about −2° C. to about 60° C., 0° C. to about 60° C., or 4°C. to about 60° C., e.g., about −2° C.-0° C., 0° C.-4° C., 4° C.-5° C.,4° C.-5° C., 5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C.,25° C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50°C., 50° C.-55° C., or 55° C.-60° C. In still other embodiments, thefirst reagent and the second reagent are configured to be contacted witheach other to form a liquid, e.g., a solution, that comprisesperoxyformic acid at a temperature at about 4° C. or lower than 4° C.,e.g., at about 3° C., 2° C., 1° C., 0° C., or lower than 0° C.

The solid composition can be configured to be contacted with a liquid toform a liquid, e.g., a solution, that comprises peroxyformic acid underany suitable conditions or temperature. In some embodiments, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises peroxyformic acid under ambientconditions. In other embodiments, the solid composition can beconfigured to be contacted with a liquid to form a liquid, e.g., asolution, that comprises peroxyformic acid at a temperature ranging fromabout −2° C. to about 60° C., 0° C. to about 60° C., or 4° C. to about60° C., e.g., about −2° C.-0° C., 0° C.-4° C., 4° C.-5° C., 4° C.-5° C.,5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C., 25° C.-30°C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50° C., 50°C.-55° C., or 55° C.-60° C. In still other embodiments, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises peroxyformic acid at atemperature at about 4° C. or lower than 4° C., e.g., at about 3° C., 2°C., 1° C., 0° C., or lower than 0° C.

The present peroxyformic acid forming compositions can comprise anysuitable concentration of an ester of a polyhydric alcohol and formicacid. For example, the first reagent of the peroxyformic acid formingcomposition can comprise any suitable concentration of an ester of apolyhydric alcohol and formic acid. In some embodiments, the formedliquid is a concentrate and comprises the first reagent in an amount upto about 90% of an ester of a polyhydric alcohol and formic acid. Inother embodiments, the formed liquid comprises the first reagent in anamount from about 1 ppm to about 500,000 ppm of an ester of a polyhydricalcohol and formic acid, or from about 10 ppm to about 500,000 ppm of anester of a polyhydric alcohol and formic acid. For example, the firstreagent in the formed liquid can comprise from about 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm,5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm,7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm,10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm,80,000-90,000 ppm, 90,000-100,000 ppm, 100,000-150,000 ppm,150,000-200,000 ppm, 200,000-250,000 ppm, 250,000-300,000 ppm,300,000-350,000 ppm, 350,000-400,000 ppm, 400,000-450,000 ppm, or450,000-500,000 ppm. In other embodiments, the first reagent in theformed liquid can comprise from about 50 ppm to about 40,000 ppm of anester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

In another example, the solid composition of the peroxyformic acidforming composition can comprise any suitable concentration of an esterof a polyhydric alcohol and formic acid. In some embodiments, the solidcomposition can provide a concentrate formed liquid that comprises thefirst reagent in an amount up to about 90% of an ester of a polyhydricalcohol and formic acid. In other embodiments, the solid composition canprovide for the formed liquid from about 10 ppm to about 500,000 ppm ofan ester of a polyhydric alcohol and formic acid. For example, the solidcomposition can provide for the formed liquid the ester of a polyhydricalcohol and formic acid in amounts comprising from about 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm,5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm,7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm,10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm,80,000-90,000 ppm, 90,000-100,000 ppm, 100,000-150,000 ppm,150,000-200,000 ppm, 200,000-250,000 ppm, 250,000-300,000 ppm,300,000-350,000 ppm, 350,000-400,000 ppm, 400,000-450,000 ppm, or450,000-500,000 ppm. In other embodiments, the solid composition canprovide for the formed liquid from about 50 ppm to about 40,000 ppm ofan ester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

The present peroxyformic acid forming compositions can comprise anysuitable concentration of hydrogen peroxide or a substance thatgenerates hydrogen peroxide upon contact with a liquid. For example, thesecond reagent of the peroxyformic acid forming composition can compriseany suitable concentration of hydrogen peroxide. In some embodiments, aconcentrate formed liquid comprises the second reagent in an amount upto about 10% of hydrogen peroxide. In some embodiments, the formedliquid comprises the second reagent in an amount comprising about 0.1ppm to about 100,000 ppm of hydrogen peroxide, or about 0.1 ppm to about100,000 ppm of hydrogen peroxide. For example, the second reagent in theformed liquid can comprise from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm,20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm,300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm,850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm,20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or90,000-100,000 ppm, 100,000-150,000 ppm, 150,000-200,000 ppm,200,000-250,000 ppm, or 250,000-300,000 ppm hydrogen peroxide. In otherembodiments, the second reagent in the formed liquid comprises fromabout 150 ppm to about 50,000 ppm of hydrogen peroxide, e.g., about150-200, 150-300, 150-400, 150-500, 150-600, 150-700, 150-800, 150-900,150-1,000, 150-1,500, 150-2,000, 150-2,500, 150-3,000, 150-3,500,150-4,000, 150-4,500, 150-5,000, 150-10,000, 50-20,000, 50-30,000,50-40,000 or 50-50,000 ppm of hydrogen peroxide.

In some embodiments, a concentrate formed liquid comprises the secondreagent in an amount up to about 10% of hydrogen peroxide. In anotherexample, the solid composition can comprise a substance at an amount orconcentration that generates from about 0.1 ppm to about 100,000 ppm ofhydrogen peroxide upon contact with a liquid in the formed liquid. Forexample, the solid composition can comprise a substance at an amount orconcentration that generates from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm,20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm,300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm,850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm,20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or90,000-100,000 ppm hydrogen peroxide.

The present peroxyformic acid forming compositions can be configured toform a liquid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid. For example, the first reagent andthe second reagent in the present peroxyformic acid forming compositionscan be configured to be contacted with each other to form a liquidand/or solid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid. In some embodiments, the firstreagent and the second reagent can be configured to be contacted witheach other to form a liquid, e.g., a solution, that comprises from about0.1 ppm to about 100,000 ppm of peroxyformic acid, from about 0.1 ppm toabout 10,000 ppm of peroxyformic acid, or from about 0.1 ppm to about5,000 ppm of peroxyformic acid, e.g., about 0.1-1 ppm, 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, or 4,500-5,000 ppm or greater ofperoxyformic acid. In other embodiments, the first reagent and thesecond reagent can be configured to be contacted with each other to forma liquid, e.g., a solution, that comprises from about 1 ppm to about 500ppm of peroxyformic acid, e.g., about 0.1-1 ppm, 0.1-10 ppm, 0.1-20 ppm,0.1-30 ppm, 0.1-40 ppm, 0.1-50 ppm, 0.1-60 ppm, 0.1-70 ppm, 0.1-80 ppm,0.1-90 ppm, 0.1-100 ppm, 0.1-150 ppm, 0.1-200 ppm, 0.1-250 ppm, 0.1-300ppm, 0.1-350 ppm, 0.1-400 ppm, 0.1-450 ppm, 0.1-500 ppm of peroxyformicacid. In still other embodiments, the first reagent and the secondreagent can be configured to be contacted with each other to form aliquid, e.g., a solution, that comprises from about 50 ppm to about 100ppm of peroxyformic acid, e.g., about 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm or 90-100 ppm of peroxyformic acid. In yet other embodiments,the first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises from about 200 ppm to about 300 ppm of peroxyformic acid,e.g., about 200-210 ppm, 210-220 ppm, 220-230 ppm, 230-240 ppm, 240-250ppm, 250-260 ppm, 260-270 ppm, 270-280 ppm, 280-290 ppm, 290-300 ppm ofperoxyformic acid.

In an aspect, at least about 1 ppm peroxyformic is generated within lessthan 1 minute of contacting the first reagent and the second reagent. Inan aspect, at least about 1 ppm peroxyformic is generated within lessthan about 55 seconds, 50 seconds or less, 45 seconds or less, 40seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds orless, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5seconds or less. In an aspect, the reaction to form a liquid comprisingat least about 1 ppm peroxyformic acid is near instantaneous.

Additional Peracids

The peroxyformic acid formed using the present methods (presentcomposition) can further comprise other percarboxylic acids. A peracidincludes any compound of the formula R—(COOOH)_(n) in which R can behydrogen, alkyl, alkenyl, alkyne, acylic, alicyclic group, aryl,heteroaryl, or heterocyclic group, and n is 1, 2, or 3, and named byprefixing the parent acid with peroxy. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined herein. Various embodiments of the invention referring toperoxyformic acid compositions and/or peroxyformic acid solutions arefurther understood to optionally comprise additional percarboxylicacids. As used herein, the term “peracid” may also be referred to as a“percarboxylic acid” or “peroxyacid.” Sulfoperoxycarboxylic acids,sulfonated peracids and sulfonated peroxycarboxylic acids are alsoincluded within the term “peracid” as used herein. The terms“sulfoperoxycarboxylic acid,” “sulfonated peracid,” or “sulfonatedperoxycarboxylic acid” refers to the peroxycarboxylic acid form of asulfonated carboxylic acid as disclosed in U.S. Patent Publication Nos.2010/0021557, 2010/0048730 and 2012/0052134 which are incorporatedherein by reference in their entireties. A peracid refers to an acidhaving the hydrogen of the hydroxyl group in carboxylic acid replaced bya hydroxy group. Oxidizing peracids may also be referred to herein asperoxycarboxylic acids.

In other embodiments, a mixed peracid is employed, such as aperoxycarboxylic acid including at least one peroxycarboxylic acid oflimited water solubility in which R includes alkyl of 5-22 carbon atomsand at least one water-soluble peroxycarboxylic acid in which R includesalkyl of 1-4 carbon atoms. For example, in one embodiment, aperoxycarboxylic acid includes peroxyacetic acid and at least one otherperoxycarboxylic acid such as those named above. Preferably acomposition of the invention includes peroxyformic acid, peroxyaceticacid and/or peroxyoctanoic acid. Other combinations of mixed peracidsare well suited for use in the current invention. Advantageously, acombination of peroxycarboxylic acids provides a composition withdesirable antimicrobial activity in the presence of high organic soilloads. The mixed peroxycarboxylic acid compositions often providesynergistic micro efficacy. Accordingly, compositions of the inventioncan include a peroxycarboxylic acid, or mixtures thereof.

Water

The peroxyformic acid compositions according to the invention maycomprise water in amounts that vary depending upon techniques forprocessing the composition. Water provides a medium which dissolves,suspends, or carries the other components of the composition. Water canalso function to deliver and wet the composition of the invention on anobject.

In some embodiments, water makes up a large portion of the compositionof the invention and may be the balance of the composition apart fromperoxyformic acid composition. The water amount and type will dependupon the nature of the composition as a whole, the environmentalstorage, and method of application including concentration composition,form of the composition, and intended method of delivery, among otherfactors. Notably the carrier should be chosen and used at aconcentration which does not inhibit the efficacy of the functionalcomponents in the composition of the invention for the intended use.

Additional Functional Ingredients

The components of the peroxyformic acid compositions can further becombined with various functional components suitable for use in membranetreatment. In some embodiments, the peroxyformic acid compositions makeup a large amount, or even substantially all of the treatmentcomposition for the membranes as disclosed herein. For example, in someembodiments few or no additional functional ingredients are disposedtherein.

In other embodiments, additional functional ingredients may be includedin the compositions. The functional ingredients provide desiredproperties and functionalities to the compositions. For the purpose ofthis application, the term “functional ingredient” includes a materialthat when dispersed or dissolved in a use and/or concentrate solution,such as an aqueous solution, provides a beneficial property in aparticular use. Some particular examples of functional materials arediscussed in more detail below, although the particular materialsdiscussed are given by way of example only, and that a broad variety ofother functional ingredients may be used.

In some embodiments, the peroxyformic acid compositions may includesurfactants, such as for example nonionic and anionic surfactants,defoaming agents, anti-redeposition agents, bleaching agents, solubilitymodifiers, dispersants, rinse aids, metal protecting agents, stabilizingagents, corrosion inhibitors, sequestrants and/or chelating agents,wetting agents, water conditioning agents or chelants, enzymes,fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes orcouplers, buffers, solvents and the like.

Builders

The present compositions can include a builder. Builders includechelating agents (chelators), sequestering agents (sequestrants), andthe like. The builder may act to stabilize the cleaning composition oruse solution. Examples of builders include, but are not limited to,phosphonates, phosphates, aminocarboxylates and their derivatives,pyrophosphates, polyphosphates, ethylenediamene and ethylenetriamenederivatives, hydroxyacids, and mono-, di-, and tri-carboxylates andtheir corresponding acids. Other exemplary builders includealuminosilicates, nitroloacetates and their derivatives, and mixturesthereof. Still other exemplary builders include aminocarboxylates,including salts of ethylenediaminetetraacetic acid (EDTA),hydroxyethylenediaminetetraacetic acid (HEDTA), anddiethylenetriaminepentaacetic acid. For a further discussion ofchelating agents/sequestrants, see Kirk-Othmer, Encyclopedia of ChemicalTechnology, Third Edition, volume 5, pages 339-366 and volume 23, pages319-320, which is incorporated in its entirety. According to an aspectof the invention, preferred builders are water soluble, biodegradableand phosphorus-free. The amount of builder in the cleaning compositionor use solution, if present, is typically between about 10 ppm and about1000 ppm in the cleaning composition or use solution.

Acidulants, Catalysts and Enzymes

Acidulants may be included as additional functional ingredients in acomposition according to the invention. In an aspect, a strong mineralacid such as nitric acid, sulfuric acid, phosphoric acid or a strongerorganic acid such as methyl sulfonic acid (MSA) can be used. Thecombined use of a strong mineral acid or stronger organic acid with theperacid composition provides enhanced antimicrobial efficacy. Inaddition, some strong mineral and organic acids, such as nitric acid,provide a further benefit of reducing the risk of corrosion towardmetals contacted by the peracid compositions according to the invention.In some embodiments, the present composition does not comprise a mineralacid or a strong mineral acid.

In an aspect, the methods of forming the peroxyformic acid may beconducted in the presence of a catalyst. Any suitable catalyst can beused in the present methods. In some embodiments, the catalyst can be amineral or strong organic acid, e.g., sulfuric acid, methanesulfonicacid, nitric acid, phosphoric acid, pyrophosphoric acid, polyphosphoricacid or phosphonic acid. Such catalysts may be present in peroxyformicacid forming composition in an amount of at least about 0 wt-% to about10 wt-%, preferably at least about 0.1 wt-% to about 5 wt-%, morepreferably from about 1 wt-% to about 5 wt-%.

In some aspects, the present methods can further comprise using acatalyst or an enzyme that catalyzes formation of peroxyformic acid,such as from the ester of a polyhydric alcohol and formic acid, andhydrogen peroxide. The present methods can use any suitable catalyst orenzyme, e.g., a perhydrolytic enzyme, lipase, coronase, termanyl oresperease. The catalyst or an enzyme can be comprised in any suitablereagent. In some embodiments, the first reagent comprises the catalystor enzyme. In other embodiments, the second reagent comprises thecatalyst or enzyme. In still other embodiments, the present methods canfurther comprise using a third reagent that comprises the catalyst orenzyme. In yet other embodiments, the solid composition comprises thecatalyst or enzyme.

Acidulants, catalysts and/or enzymes may be employed in amountssufficient in a use solution in an amount of at least about 0.1 wt-% toabout 10 wt-%, preferably at least about 0.1 wt-% to about 5 wt-%, morepreferably from about 0.1 wt-% to about 1 wt-%.

Catalase and Peroxidase Enzyme

In an aspect of the invention, a catalase or peroxidase enzyme can beused to reduce and/or eliminate the concentration of hydrogen peroxidein an antimicrobial peracid composition. The enzymes catalyze thedecomposition of hydrogen peroxide to water and oxygen.

Various sources of catalase enzymes may be employed according to theinvention, including: animal sources such as bovine catalase isolatedfrom beef livers; fungal catalases isolated from fungi includingPenicillium chrysogenum, Penicillium notatum, and Aspergillus niger;plant sources; bacterial sources such as Staphylococcus aureus, andgenetic variations and modifications thereof. In an aspect of theinvention, fungal catalases are utilized to reduce the hydrogen peroxidecontent of a peracid composition. Catalases are commercially availablein various forms, including liquid and spray dried forms. Commerciallyavailable catalase includes both the active enzyme as well as additionalingredients to enhance the stability of the enzyme. Some exemplarycommercially available catalase enzymes include Genencor CA-100 andCA-400, as well as Mitsubishi Gas and Chemical (MGC) ASC super G and ASCsuper 200, and Optimase CA 400L from Genecor International. Additionaldescription of suitable catalase enzymes are disclosed and hereinincorporated by reference in its entirety from U.S. Patent PublicationNo. 2009/0269324.

In an aspect of the invention, catalase enzymes have a high ability todecompose hydrogen peroxide. Beneficially, the reduction or eliminationof hydrogen peroxide from oxidizing compositions obviates the variousdetriments caused by oxidizing agents. In particular, the use ofcatalase with the peracids compositions provides enhanced antimicrobialbenefits without causing the damage associated with conventionaloxidizing agents (e.g. peracetic acid, hypochlorite or hypochlorousacid, and/or chlorine dioxide), such as corrosion.

Peroxidase enzymes may also be employed to decompose hydrogen peroxidefrom a peracid composition. Although peroxidase enzymes primarilyfunction to enable oxidation of substrates by hydrogen peroxide, theyare also suitable for effectively lowering hydrogen peroxide to peracidratios in compositions. Various sources of peroxidase enzymes may beemployed according to the invention, including for example animalsources, fungal peroxidases, and genetic variations and modificationsthereof. Peroxidases are commercially available in various forms,including liquid and spray dried forms. Commercially availableperoxidases include both the active enzyme as well as additionalingredients to enhance the stability of the enzyme.

In some embodiments, the catalase or peroxidase enzyme is able todegrade at least about 50% of the initial concentration of hydrogenperoxide in a peracid composition. Preferably, the enzyme is provided insufficient amount to reduce the hydrogen peroxide concentration of aperacid composition by at least more than about 50%, more preferably atleast about 60%, at least about 70%, at least about 80%, at least about90%. In some embodiments, the enzyme reduces the hydrogen peroxideconcentration of a peracid composition by more than 90%.

In an aspect of the invention, the enzymes are suitable for use and havea tolerance to a wide range of temperatures, including the temperaturesranges in water treatment applications which may range from about 0-80°C. A suitable catalase enzyme will maintain at least 50% of its activityunder such storage and/or application temperatures for at least about 10minutes, preferably for at least about 1 hour.

In an aspect of the invention, a catalase or peroxidase enzyme ispresent in a use solution of the peracid composition in sufficientamounts to reduce the concentration of hydrogen peroxide from theperacid composition by at least 50% within about 10 minutes, preferablywithin about 5 minutes, preferably within about 2 to 5 minutes, morepreferably within about 1 minute. The ranges of concentration of theenzymes will vary depending upon the amount of time within which 50% ofthe hydrogen peroxide from the peracid composition is removed. Incertain aspects of the invention, a catalase or peroxidase enzyme ispresent in a use solution composition including the water source to betreated in amounts between about 1 ppm and about 1,000 ppm, preferablybetween about 5 ppm and 500 ppm, and more preferably between about 10ppm and about 100 ppm.

Defoaming Agents

In an aspect of the invention, a defoaming agent, which can includesurfactants and polymers can be used to reduce and/or eliminate foamingin the cleaning of the surfaces disclosed according to the invention.Examples of defoaming agents include, but are not limited to: ethyleneoxide/propylene block copolymers such as those available under the namePluronic N-3; silicone compounds such as silica dispersed inpolydimethylsiloxane, polydimethylsiloxane, and functionalizedpolydimethylsiloxane such as those available under the name Abil B9952;fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fattyalcohols, fatty acid soaps, ethoxylates, mineral oils, polyethyleneglycol esters, and alkyl phosphate esters such as monostearyl phosphate.A discussion of defoaming agents may be found, for example, in U.S. Pat.No. 3,048,548 to Martin et al., U.S. Pat. No. 3,334,147 to Brunelle etal., and U.S. Pat. No. 3,442,242 to Rue et al., the disclosures of whichare incorporated herein by reference.

In an aspect, various polymers are suitable for use as defoaming agents,including for example polyoxyethylene-polyoxypropylene block copolymer.Particularly preferred defoaming agents include nonionic blockcopolymers having the general structure: polyoxypropylene core withpolyoxyethylene caps

Defoaming agents can include surfactants and polymers employed inamounts sufficient in a use solution in an amount of at least about 0.01wt-% to about 30 wt-%, preferably at least about 0.1 wt-% to about 20wt-%, more preferably from about 0.1 wt-% to about 10 wt-%.

Surfactants

The surfactants described hereinabove can be used singly or incombination with the methods of the present invention. In particular,the nonionics and anionics can be used in combination. The semi-polarnonionic, cationic, amphoteric and zwitterionic surfactants can beemployed in combination with nonionics or anionics. The above examplesare merely specific illustrations of the numerous surfactants which canfind application within the scope of this invention. It should beunderstood that the selection of particular surfactants or combinationsof surfactants can be based on a number of factors includingcompatibility with the membrane at the intended use concentration andthe intended environmental conditions including temperature and pH.Accordingly, one should understand that surfactants that may damage aparticular membrane during conditions of use should not be used withthat membrane. It is expected that the same surfactant, however, may beuseful with other types of membranes. In addition, the level and degreeof foaming under the conditions of use and in subsequent recovery of thecomposition can be a factor for selecting particular surfactants andmixtures of surfactants. For example, in certain applications it may bedesirable to minimize foaming and, as a result, one would select asurfactant or mixture of surfactants that provides reduced foaming. Inaddition, it may be desirable to select a surfactant or a mixture ofsurfactants that exhibits a foam that breaks down relatively quickly sothat the composition can be recovered and reused with an acceptableamount of down time. In addition, the surfactant or mixture ofsurfactants can be selected depending upon the particular soil that isto be removed.

It should be understood that the compositions for use with the methodsof the present invention need not include a surfactant or a surfactantmixture, and can include other components. In addition, the compositionscan include a surfactant or surfactant mixture in combination with othercomponents. Exemplary additional components that can be provided withinthe compositions include builders, water conditioning agents,non-aqueous components, adjuvants, carriers, processing aids, enzymes,and pH adjusting agents. When surfactants are included in theperoxyformic acid compositions in a use solution they can be included inan amount of at least about 0.1 wt. % to about 10 wt. %.

Anionic Surfactants

The peroxyformic acid compositions can contain a surfactant component(s)that includes a detersive amount of an anionic surfactant or a mixtureof anionic surfactants. Anionic surfactants are desirable in cleaningcompositions because of their wetting, detersive properties, and oftentimes good compatibility with membranes. The anionic surfactants thatcan be used according to the invention include any anionic surfactantavailable in the cleaning industry. Suitable groups of anionicsurfactants include sulfonates and sulfates. Suitable surfactants thatcan be provided in the anionic surfactant component include alkyl arylsulfonates, secondary alkane sulfonates, alkyl methyl ester sulfonates,alpha olefin sulfonates, alkyl ether sulfates, alkyl sulfates, andalcohol sulfates. Suitable alkyl aryl sulfonates that can be used in thecleaning composition can have an alkyl group that contains 6 to 24carbon atoms and the aryl group can be at least one of benzene, toluene,and xylene. A suitable alkyl aryl sulfonate includes linear alkylbenzene sulfonate. A suitable linear alkyl benzene sulfonate includeslinear dodecyl benzyl sulfonate that can be provided as an acid that isneutralized to form the sulfonate. Additional suitable alkyl arylsulfonates include xylene sulfonate and cumene sulfonate. Suitablealkane sulfonates that can be used in the cleaning composition can havean alkane group having 6 to 24 carbon atoms. Suitable alkane sulfonatesthat can be used include secondary alkane sulfonates. A suitablesecondary alkane sulfonate includes sodium C14-C17 secondary alkylsulfonate. Suitable alkyl methyl ester sulfonates that can be used inthe cleaning composition include those having an alkyl group containing6 to 24 carbon atoms. Suitable alpha olefin sulfonates that can be usedin the cleaning composition include those having alpha olefin groupscontaining 6 to 24 carbon atoms. Suitable alkyl ether sulfates that canbe used in the cleaning composition include those having between about 1and about 10 repeating alkoxy groups, between about 1 and about 5repeating alkoxy groups. In general, the alkoxy group will containbetween about 2 and about 4 carbon atoms. A suitable alkoxy group isethoxy. A suitable alkyl ether sulfate is sodium lauryl ether ethoxylatesulfate. Suitable alkyl sulfates that can be used in the cleaningcomposition include those having an alkyl group containing 6 to 24carbon atoms. Suitable alkyl sulfates include, but are not limited to,sodium lauryl sulfate and sodium lauryl/myristyl sulfate. Suitablealcohol sulfates that can be used in the cleaning composition includethose having an alcohol group containing about 6 to about 24 carbonatoms.

Further examples of suitable anionic surfactants are given in “SurfaceActive Agents and Detergents” (Vol. I and II by Schwartz, Perry andBerch). A variety of such surfactants are also generally disclosed inU.S. Pat. No. 3,929,678. The disclosures of the above referencesrelating to anionic surfactants are incorporated herein by reference.

Nonionic Surfactants

The peroxyformic acid compositions can contain a surfactant component(s)that includes a detersive amount of an nonionic surfactant or a mixtureof nonionic surfactants. Nonionic surfactants can be included in thecomposition to enhance soil removal properties. Nonionic surfactantsuseful in the invention are generally characterized by the presence ofan organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties.

Nonionic surfactants that can be used in the composition includepolyalkylene oxide surfactants (also known as polyoxyalkylenesurfactants or polyalkylene glycol surfactants). Suitable polyalkyleneoxide surfactants include polyoxypropylene surfactants andpolyoxyethylene glycol surfactants. Suitable surfactants of this typeare synthetic organic polyoxypropylene (PO)-polyoxyethylene (EO) blockcopolymers. These surfactants include a di-block polymer comprising anEO block and a PO block, a center block of polyoxypropylene units (PO),and having blocks of polyoxyethylene grafted onto the polyoxypropyleneunit or a center block of EO with attached PO blocks. Further, thissurfactant can have further blocks of either polyoxyethylene orpolyoxypropylene in the molecules. A suitable average molecular weightrange of useful surfactants can be about 1,000 to about 40,000 and theweight percent content of ethylene oxide can be about 10-80 wt. %.

Additional nonionic surfactants include alcohol alkoxylates. An suitablealcohol alkoxylate include linear alcohol ethoxylates. Additionalalcohol alkoxylates include alkylphenol ethoxylates, branched alcoholethoxylates, secondary alcohol ethoxylates, castor oil ethoxylates,alkylamine ethoxylates, tallow amine ethoxylates, fatty acidethoxylates, sorbital oleate ethoxylates, end-capped ethoxylates, ormixtures thereof. Additional nonionic surfactants include amides such asfatty alkanolamides, alkyldiethanolamides, coconut diethanolamide,lauramide diethanolamide, cocoamide diethanolamide, polyethylene glycolcocoamide, oleic diethanolamide, or mixtures thereof. Additionalsuitable nonionic surfactants include polyalkoxylated aliphatic base,polyalkoxylated amide, glycol esters, glycerol esters, amine oxides,phosphate esters, alcohol phosphate, fatty triglycerides, fattytriglyceride esters, alkyl ether phosphate, alkyl esters, alkyl phenolethoxylate phosphate esters, alkyl polysaccharides, block copolymers,alkyl glucosides, or mixtures thereof.

Other exemplary nonionic surfactants for use with the methods of thepresent invention are disclosed in the treatise Nonionic Surfactants,edited by Schick, M. J., Vol. 1 of the Surfactant Science Series, MarcelDekker, Inc., New York, 1983, the contents of which is incorporated byreference herein. A typical listing of nonionic classes, and species ofthese surfactants, is also given in U.S. Pat. No. 3,929,678. Furtherexamples are given in “Surface Active Agents and Detergents” (Vol. I andII by Schwartz, Perry and Berch). The disclosures of these referencesrelating to nonionic surfactants are incorporated herein by reference.

Amphoteric Surfactants

Amphoteric surfactants can also be used to provide desired detersiveproperties. Amphoteric, or ampholytic, surfactants contain both a basicand an acidic hydrophilic group and an organic hydrophobic group. Theseionic entities may be any of anionic or cationic groups described hereinfor other types of surfactants. A basic nitrogen and an acidiccarboxylate group are the typical functional groups employed as thebasic and acidic hydrophilic groups. In a few surfactants, sulfonate,sulfate, phosphonate or phosphate provide the negative charge. Suitableamphoteric surfactants include, but are not limited to: sultaines,amphopropionates, amphodipropionates, aminopropionates,aminodipropionates, amphoacetates, amphodiacetates, andamphohydroxypropylsulfonates.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphato, or phosphono. Amphoteric surfactants are subdivided into twomajor classes. The first class includes acyl/dialkyl ethylenediaminederivatives (e.g. 2-alkyl hydroxyethyl imidazoline derivatives) andtheir salts. The second class includes N-alkylamino acids and theirsalts. Some amphoteric surfactants can be envisioned as fitting intoboth classes.

Zwitterionic Surfactants

In some embodiments, zwitterionic surfactants are used with the methodsof the invention. Zwitterionic surfactants can be thought of as a subsetof the amphoteric surfactants. Zwitterionic surfactants can be broadlydescribed as derivatives of secondary and tertiary amines, derivativesof heterocyclic secondary and tertiary amines, or derivatives ofquaternary ammonium, quaternary phosphonium or tertiary sulfoniumcompounds. Typically, a zwitterionic surfactant includes a positivecharged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionics generally contain cationic and anionic groups which ionizeto a nearly equal degree in the isoelectric region of the molecule andwhich can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate. Betaine and sultaine surfactants areexemplary zwitterionic surfactants for use herein.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678. Further examples aregiven in “Surface Active Agents and Detergents” (Vol. I and II bySchwartz, Perry and Berch). The disclosures of zwitterionic surfactantsin the above references are incorporated herein by reference.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

The materials used in the following Examples are provided herein:

Various commercially-available stock solutions were employed informulations (available from various sources) including: methanesulfonic acid (70%), linear alkylbenzene sulphonates (96%), sodiumxylene sulfonate (40%), formic acid (85%), and hydrogen peroxide (50%).

POAA: a commercial product containing 5.25 to 6.4% peroxyacetic acid and25.6 to 29.4% H₂O₂.

Exemplary peroxyformic acid compositions generated in situ and employedin some of the Examples are listed in the Table 1 below:

TABLE 1 PFA-30-1 PFA-30-2 30-3 Component (wt %) (wt %) (wt %) Water 0.000.00 16.25 MSA (70%) 3.0 3.0 3.0 LAS (96%) 4.93 0 4.93 Formic acid (85%)75.82 80.75 75.82 H₂O₂ (50%) 16.25 16.25 0 Total 100.00 100.00 100.00PFA (5 min after mixing) 10.19% 9.22% 0.00%

The peroxyformic acid compositions shown in Table 1 were made from a twopart system. Part A provided the formic acid and optionally with otheringredients excluding the H₂O₂. Part B for the formulations PFA 30-1 andPFA 30-2 provided H₂O₂ and optionally with other ingredients excludingthe formic acid provided in Part A. On mixing Part A and Part B underambient conditions, peroxyformic acid (PFA) reached maximum level within5 min., i.e. the compositions were ready to use. Composition 30-3 is aformic acid composition and not a peroxyformic acid composition.

Accordingly, the peroxyformic acid formed provides a superior biocideagainst microorganisms, especially spores and biofilms suitable for theuses disclosed herein according to the embodiments of the invention.

Example 1

The removal of biofilm was tested to determine efficacy of biofilmremoval and kill rates of Pseudomonas aeruginosa. Pseudomonas arewell-known as common ‘pioneer’ bacteria and often tested forbiofilm-inhibiting agents' effectivity. The bacteria are known toexcrete polysaccharides and generate biofilm on a variety of surfacesvery rapidly (including, for example, membrane filtration elements), aswell as commonly demonstrate resistance to various antimicrobialcompositions. However, bacteria that exist in a biofilm arephenotypically different from suspended cells of the same genotype;therefore the study of biofilm in the laboratory requires protocols thataccount for this difference. Laboratory biofilms are engineered ingrowth reactors designed to produce a specific biofilm type. Alteringsystem parameters correspondingly results in a change in the biofilm.

Pseudomonas aeruginosa (ATCC 700888) was the organism used. An isolatedcolony was aseptically removed from an R2A plate and placed into 100 mlof sterile bacterial liquid growth broth (300 mg/L) and incubated in anenvironmental shaker at 35° C. for 20-24 hours. Viable bacterial densityshould equal 108 CFU/ml, and may be checked by serial dilution andplating. Pseudomonas aeruginosa were grown in a CDC reactor system for48 hours at room temperature. See Goeres, D. M., et al., Statisticalassessment of a laboratory method for growing biofilms, Microbiology151:757-762 (2005). Biofilm challenge is approximately 8 logs throughouttesting from a 48 hour growth.

Biofilms were prepared on membrane surfaces for evaluation. Small KochHFK-131 UF membrane rectangles were prepared by punching out a spiralwound membrane and placing the membrane disk into a plastic rectangleused to serve as “framing material”. The membranes were placed into theCDC rod and used for testing. After the biofilm was developed, themembrane rectangles were removed and placed into a sterile plasticcentrifuge tube. Each exemplary composition was pipette into thecentrifuge tube in duplicate and exposed to the membrane rectangles forthe specified exposure time (5 or 10 minutes) at room temperature. Afterthe specified exposure time the solutions were neutralized inNeutralizer Broth, vortexed, sonicated, serially diluted and plated forplate counts. The average log reduction for each evaluated compositionwas obtained as follows: peroxyformic acid (Formulations 30-1 and 30-2),untreated control not containing peroxyformic acid (Formulation 30-3),and a known antimicrobial composition (Oxonia Active). The results ofthese experiments are shown in FIG. 1 .

As can be seen in FIG. 1 , all three exemplary compositions efficientlyreduced Pseudomonas aeruginosa biofilm at the indicated exposure times.Compositions 30-1 and 30-2 at the concentration of 0.3% (product)provide significant log reduction in (>6.68) at both the 5 and 10 minuteexposure times, while the average log reduction for composition 30-3containing formic acid alone (4.15 at 5 minutes and 3.02 at 10 minutes)has significantly less efficacy against the test microorganism. At leasta 3 log reduction in the biofilm organisms is conventionally required asa commercial threshold for biofilm treatments to comply with EPArequirements. Accordingly, the PFA compositions according to theinvention provide suitable compositions for biofilm treatment.Accordingly, the peroxyformic acid formed provides a superior biocideagainst microorganisms, especially spores and biofilms suitable for theuses disclosed herein according to the embodiments of the invention.

Example 2

Mesophilic bacterial endospores (also referred to as spores in thisExample) were further evaluated for the efficacy of peroxyformic acid orremoval and kill rates. The procedure outlined in Example 1 was followedreplacing Pseudomonas aeruginosa with field isolates of mesophilicspores against varying concentrations of actives of the peroxyformicacid according to a lower active concentration (0.15% PFA composition30-1 and 0.2% PFA composition 30-1) at a 5 minute exposure time andcompared to peroxyacetic acid compositions (0.2% or 0.25% of peraceticacid compositions). The results of these experiments are shown in FIG. 2.

As illustrated in FIG. 2 , both concentrations (0.15% and 0.2%) offormulas 30-1 and 30-2 were particularly effective in reducingmesophilic spores at a 5 minute exposure time at a lower activesconcentration than what was evaluated in Example 1. Composition 30-3(0.15% and 0.2%) showed comparable log reduction with peracetic acidcomposition.

Example 3

Reduction of P. aeruginosa Biofilm Using Different Exposure Times ofPeroxyformic Acid. P. aeruginosa ATCC 15442 biofilm was grown on thesurface of 24 polycarbonate coupons following ASTM method E2562-12:Standard Test Method for Quantification of Pseudomonas aeruginosaBiofilm Grown with High Shear and Continuous Flow using CDC BiofilmReactor. After 48 hours of biofilm establishment, the coupons wereremoved from the reactor and placed into individual centrifuge tubes.Three coupons per test condition were tested for disinfectant efficacyusing ASTM method E2871-12: Standard Test Method for EvaluatingDisinfectant Efficacy against Pseudomonas aeruginosa Biofilm Grown inCDC Biofilm Reactor using Single Tube Method. Sets of three coupons wereexposed to 4 mL of 50 ppm PFA for exposure times of 15 minutes, 30minutes, 1 hour, 2 hours and 3 hours, while coupons treated with 200 ppmPOAA were exposed for 3 hours only. After the desired exposure time, 16mL of neutralizing medium was added on top of the chemistry to inactiveantimicrobial performance. This was followed with a series of vortexingand sonicating steps to remove any biofilm from the coupon surface intothe solution for plating and enumeration. As shown in FIG. 3 ,peroxyformic acid achieves greater anti-biofilm efficacy with shorterexposure time and lower concentrations than POAA.

Example 4

Additional biocidal performance of performic acid was evaluated for logreduction of Pseudomonas aeruginosa as shown in Table 2.

TABLE 2 Test Systems: Pseudomonas aeruginosa ATCC 15442 Test Substance500 ppm synthetic hard water, pH 7.74 Diluents: Test A. 0.5 ppm PFA: 47μL PFA Concentrate (0.107% PFA)/99 mL diluent Substances: pH 6.71 B. 1.0ppm PFA: 93 μL PFA Concentrate (0.107% PFA)/99 mL diluent pH 6.31 C. 2.0ppm PFA: 185 μL PFA Concentrate (0.107% PFA)/99 mL diluent pH 5.34Exposure 10 minutes and 4 hours Time(s): Neutralizer: 9 mL DE Broth Test25° C. Temperature Plating TGE Medium: Incubation: 35° C. for 48 hours

FIG. 4 shows the results of biocidal efficacy after 10 minutes contactand 4 hours contact showing the beneficially efficacy of performic acidgenerated in situ according to the invention at varying concentrations.

Example 5

Additional biocidal performance of performic acid was evaluated for logreduction of Pseudomonas aeruginosa in comparison to another peroxyacid.A Pseudomonas biofilm was treated with 50 ppm active of PFA and comparedto efficacy treated with 200 ppm PAA. Pseudomonas biofilms were grown ina CDC biofilm reactor on a poly carbonate coupons. Appropriateconcentration of the treatment substance were diluted in hard water atpH 7.71 diluent. Test chemicals were exposed for 3 hrs after which theywere treated with 16 mLs of thiosulfate to neutralize any oxidants. Theuntreated control and treated Pseudomonas were plated on a TGE media andincubated at 35° C. for 48 hrs. A 4 hr reduction was monitored by colonycounting of Pseudomonas on plates. Results are shown in FIG. 5demonstrating the beneficially efficacy of PFA generated according tothe invention. Further testing of the log reduction between decreasedconcentration of the actives of performic acid in comparison toperacetic acid is shown in FIG. 6 demonstrating the substantiallyincreased reduction in Pseudomonas aeruginosa in comparison to asubstantially higher concentration of another peroxyacid.

Example 6

Removal and/or prevention of biofilm fouling of CO₂ scrubbers was testedwith peroxyformic acid. Such scrubbers were evaluated in an ethanolfermentation plant which conventionally employs CIP cleaning processwith hot caustic recirculated through the system every few weeks toclean any biofilm which has accumulated since the prior CIP cleaningcycle. This problem to be solved is the prevention of biofilm in thesystems instead of removal of the biofilm after the same has beenformed. The prevention of biofilm is more desirable than removal, asbiofilm scuffs off and undesirably plugs lines within the system and inan fermentation facility the stream of reclaimed ethanol that goes backinto the process may undesirably carry microbes from the biofilm. As aresult, the use of performic acid was compared to the conventional CIPcleaning for efficacy.

In an exemplary treatment cycle the following conditions were employed:

Bisulfite pump cycled off;

5 minute rinse of scrubber columns with water;

Inject peroxyformic acid (PFA) for 30 minute PFA treatment at 75-100 ppmPFA at ambient temperature and at 80 gallons per minute flow(approximately 12 L/cycle treatment)—rates and intervals can varydepending on system and desired cleaning frequency;

PFA supply stops;

Restart bisulfite pump; and

Restart processing of system and rerun cycle at a predetermined amountof time (such as from as often as 3-4 hours, to weekly treatments).

According to such an exemplary embodiment, an onsite PFA generator canbe employed for generating the chemistry at a point of use. In such anembodiment for dosing directly into the scrubber columns, either formicacid or water may be employed for clearing the dosing line after the PFAis generated. In such an embodiment it is desired to employ a controllerto time the dosing of the PFA, formic acid (and/or other reagentsemployed in a generator to provide the PFA), water and bisulfite.

According to such an exemplary embodiment, it may be desired to furtheremploy a solution to neutralize or over ride the bisulfite. In analternative embodiment, the bisulfite can be discontinued (or shut off)instead of counteracting the oxidizing chemistry, according to thepreference of a user and system.

Beneficially, the use of peroxyformic acid in the CO₂ scrubbers allowedfor extended runs of the system without shutdown (for CIP cleaning),biofilm did not form, scrubber efficiency increased as measured by flow,and biofilm did not reenter the upstream processes in the plant. CO₂flow, during PFA cycles does not reduce the efficacy of treatmentcompared to alkaline treatments due to the CO₂ acting to reduce thealkalinity of sodium hydroxide and other caustic cleaners to bicarbonateand or carbonate in turn reducing the effectiveness of cleaning. SincePFA is an acidic application, this neutralization or acidification fromthe CO₂ flow is no longer an issue. The use of an onsite peroxyformicacid generator provided enhanced convenience and user-directedgeneration of the peracid.

While this invention may be embodied in many different forms, there aredescribed scientific papers, and any other referenced materialsmentioned herein are incorporated by reference in their entirety.Furthermore, the invention encompasses any possible combination of someor all of the various embodiments mentioned herein, described hereinand/or incorporated herein. In addition the invention encompasses anypossible combination that also specifically excludes any one or some ofthe various embodiments mentioned herein, described herein and/orincorporated herein.

The above disclosure is intended to be illustrative and not exhaustive.This description will suggest many variations and alternatives to one ofordinary skill in this art. All these alternatives and variations areintended to be included within the scope of the claims where the term“comprising” means “including, but not limited to”. Those familiar withthe art may recognize other equivalents to the specific embodimentsdescribed herein which equivalents are also intended to be encompassedby the claims.

What is claimed is:
 1. A method for removing microorganisms on anindustrial processing hard surface comprising: contacting the hardsurface with a peroxyformic acid composition comprising at least about25 ppm peroxyformic acid, wherein the composition is dosed on site andgenerated in situ; and removing biofilm and microbial growth from thehard surface, wherein the surface is a scrubber and/or cooling tower,tower packing materials contained in the scrubber and/or cooling tower,drain, sump, or floor.
 2. The method of claim 1, wherein the surface isa CO₂ scrubber in a fermentation system, wherein the scrubber containspacking materials, and wherein the scrubber surface and packing materialsurface is contacted with the peroxyformic acid composition in anintermittent treatment of a process water stream feeding the scrubber.3. The method of claim 1, wherein the removing of microbial growth fromthe scrubber surface prevents plugging and fouling, and enhances flow,and/or prevents biofilm formation and fouling, and wherein the treatmentwith the peroxyformic acid composition does not negatively impact thesurface being treated and does not result in residual peracid ineffluent from the system.
 4. The method of claim 1, wherein thetreatment with the peroxyformic acid composition does not contaminateany by-products from the system.
 5. The method of claim 1, furthercomprising: a pre-rinse or flushing step of washing the surface withwater, an alkaline and/or acidic solution, a step of stopping any flowof a bisulfate source (or other cleaning agent) from contacting thesurface, and/or a step of treating the surface in combination with theperoxyformic acid, before the peroxyformic acid, and/or after theperoxyformic acid, with one or more of the following agents: a defoamingcomposition, an additional sanitizing agent, an oxidant, and/or aneutralizing composition for any CO₂ on the surface.
 6. The method ofclaim 1, further comprising additional treatment cycles comprising anacidic treatment, an enzymatic treatment, an alkaline treatment and/or aneutral treatment either before or after the peroxyformic acidcomposition contacts the surface.
 7. The method of claim 1, wherein thesurface in need of treatment is contacted with from about 0.0075% toabout 0.1% active peroxyformic acid.
 8. The method of claim 1, whereinthe surface is contacted with peroxyformic acid for at least 60 secondsto about 30 minutes.
 9. The method of claim 1, wherein the surface iscontacted with peroxyformic acid on a frequency of at least once perweek.
 10. The method of claim 1, wherein the surface is contacted withthe peroxyformic acid composition at a temperature from about 2° C. to60° C.
 11. The method of claim 1, wherein the peroxyformic acidcomposition is generated in situ by contacting formic acid with hydrogenperoxide, wherein before said contacting, the ratio between theconcentration of said formic acid (w/v) and the concentration of saidhydrogen peroxide (w/v) is about 2 or higher, and the ratio between theconcentration of said peracid (w/w) and the concentration of hydrogenperoxide (w/w) in said formed resulting aqueous composition reachesabout 2 or higher within about 1 hour of said contacting.
 12. The methodof claim 11, wherein before the contacting, the formic acid is providedin a composition that comprises formic acid or a substance thatgenerates formic acid upon contact with an aqueous composition, and thehydrogen peroxide is provided in a composition that comprises hydrogenperoxide or a substance that generates hydrogen peroxide upon contactwith an aqueous composition.
 13. The method of claim 11, wherein atleast about 1% peroxyformic acid is formed in the aqueous compositionwithin about 5 minutes of the contacting.
 14. The method of claim 13,wherein the contacting of the reagents to form peroxyformic acid isconducted in the presence of a mineral acid catalyst, an acidulantand/or an enzyme.
 15. The method of claim 11, wherein the peroxyformicacid composition comprises at least one additional agent selected fromthe group consisting of a stabilizing agent, a wetting agent, asurfactant, and a defoamer.
 16. A method for removing microbial growthand mineral deposits on an industrial processing system surfacecomprising: turning off a chemical supply to the industrial processingsystem; contacting the surface with at least about 25 ppm peroxyformicacid composition generated in situ; and removing biofilm andmicroorganisms mineral deposits on the membrane, wherein the industrialprocessing system surface is a scrubber and/or cooling tower, towerpacking materials contained in the scrubber and/or cooling tower, drain,sump, or floor.
 17. The method of claim 16, wherein the surface is CO₂scrubber in a fermentation system, and wherein the scrubber surface iscontacted with the peroxyformic acid composition in an intermittenttreatment of a process water stream feeding the scrubber.
 18. The methodof claim 16, further comprising a step of stopping any flow of abisulfate source (or other cleaning agent) from contacting the surface,and/or a step of treating the surface in combination with theperoxyformic acid, before the peroxyformic acid, and/or after theperoxyformic acid, with one or more of the following agents: a defoamingcomposition, an additional sanitizing agent, an oxidant, and/or aneutralizing composition for any CO₂ on the surface.